Search

A new, simple and sensitive method for isolating nine compounds from the bisphenol group (analogues: A, B, C, E, F, G, Cl2, Z, AP) based on one-step liquid–liquid microextraction with in situ acylation followed by gas chromatography-mass spectrometry was developed and validated using influent and effluent wastewaters. The chemometric approach based on the Taguchi method was used to optimize the main conditions of simultaneous extraction and derivatization. The recoveries of the proposed procedure ranged from 85 to 122%, and the repeatability expressed by the coefficient of variation did not exceed 8%. The method’s limits of detection were in the range of 0.4–64 ng/L, and the method’s limits of quantification ranged from 1.3 to 194 ng/L. The developed method was used to determine the presence of the tested compounds in wastewater from a municipal wastewater treatment plant located in northeastern Poland. From this sample, eight analytes were detected. Concentrations of bisphenol A of 400 ng/L in influent and 100 ng/L in effluent were recorded, whereas other bisphenols reached 67 and 50 ng/L for influent and effluent, respectively. The removal efficiency of bisphenol analogues in the tested wastewater treatment plant ranged from 7 to approximately 88%.

In the presented work, phytoremediation with the use of floating plant Wolffia arrhiza (L.) Horkel ex Wimm. was proposed as a method of removing the selected benzotriazoles (BTRs): 1H-benzotriazole (1H-BTR), 4-methyl-1H-benzotriazole (4M-BTR), 5-methyl-1H-benzotriazole (5M-BTR) and 5-chlorobenzotriazole (5Cl-BTR) from water. The efficiency of phytoremediation depends on three factors: daily time of exposure to light, pH of the model solution, and the amount of plans. Using a design of experiment (DoE) methods the following optimal values were selected: plant amount 1.8 g, light exposure 13 h and pH 7 per 100 mL of the model solution. It was found that the loss of BTRs in optimal conditions ranged from 92 to 100 % except for 4M-BTR, for which only 23 % of removal was achieved after 14 days of cultivation of W. arrhiza. The half-life values for studied compounds ranged from 0.98 days for 5Cl-BTR to 36.19 for 4M-BTR. The observed rapid vanishing of 5M-BTR is supposed by the simultaneous transformation of 5M-BTR into 4M-BTR. The detailed study of BTRs degradation pointed that the plant uptake is mainly responsible for the benzotriazoles concentration decrease. Toxicity tests showed that the tested organic compounds induce oxidative stress in W. arrhiza, which manifested among others, in reduced levels of chlorophyll in cultures with benzotriazoles compared to control.

This study aimed to identify and quantify benzotriazoles (BTRs) emissions from road traffic and paved areas in an urban environment. Heterocyclic organic compounds BTRs are an emerging threat, under-recognized and under-analyzed in most environmental and water legislation. They are hazardous, potentially mutagenic, and carcinogenic micropollutants, not susceptible to effective biodegradation, and they move easily through the trophic chain, contaminating the environment and water resources. Traffic activities are a common source of BTR emissions in the urban environment, directly polluting human habitats through the different routes and numerous vehicles circulating in the cities. Using twelve heterogeneous locations scattered over a metropolitan area in Poland as a case study, this research analyzed the presence of BTRs in water samples from runoff produced from rainwater and snowmelt. 1H-BTR, 4Me-BTR, 5Me-BTR and 5Cl-BTR were detected in the tested runoff water. 5Cl-BTR was present in all samples and in the highest concentrations reaching 47,000 ng/L. Risk quotients calculated on the basis of the determined concentrations indicate that the highest environmental risk is associated with the presence of 5Cl-BTR and the sum of 4Me-BTR and 5Me-BTR, and the most sensitive organisms are bacteria and invertebrates. The results indicate that it is possible to associate the occurrence of these contaminants with the type of cover, traffic intensity, and vehicle type.

Greater awareness of micropollutants present in water and wastewater motivates the search for effective methods of their neutralization. Although their concentration in waters is measured in micro- and nanograms per liter, even at those levels, they may cause serious health consequences for different organisms, including harmful effects on the functioning of the endocrine system of vertebrates. Traditional methods of wastewater treatment, especially biological methods used in municipal wastewater treatment plants, are not sufficiently effective in removing these compounds, which results in their presence in natural waters. The growing interest in phytoremediation using constructed wetlands as a method of wastewater treatment or polishing indicates a need for the evaluation of this process in the context of micropollutant removal. Therefore, the present work presents a systematic review of the effectiveness in the removal of micropollutants from polluted waters by processes based on plant used. The article also analyzes issues related to the impact of micropollutants on the physiological processes of plants as well as changes in general indicators of pollution caused by contact of wastewater with plants. Additionally, it is also the first review of the literature that focuses strictly on the removal of micropollutants through the use of constructed wetlands.

The main aim of the paper was to assess the groundwater quality near the Municipal Solid Waste Landfill (MSW) landfill sites using landfill water pollution index (LWPI), Nemerow index (PI) and chemometric expertise. For this purpose, an analysis of eleven physicochemical parameters was performed including: pH, electrolytic conductivity (EC), total suspension (TS), chemical oxygen demand (COD), biochemical oxygen demand (BOD5), total organic carbon (TOC), dissolved organic carbon (DOC), total nitrogen (TN), total dissolved nitrogen (DN), total phosphorus (TP) and orthophosphates (OP) in landfill leachates and groundwater samples from two different MSW landfill sites in NE Poland. Research materials were collected in the period from January 2016 to May 2017. More than 80% of the data variance was explained by two factors identified by the use of principal component analysis: 44.8% was explained by the factor contributed by carbon and nitrogen-related parameters, while 35.7% by the factor contributed by phosphorus-related parameters and both, chemical and biochemical oxygen demands. The obtained results indicated negative impact of MSW landfill sites on groundwater quality which was clearly observed for samples from P1 and P4 in landfill H and for samples from P3 in landfill U.

The article presents research on the treatment of infiltration water with increased ammonium ion and nitrate(V) content through reverse osmosis. Then, research was conducted on the phenomena related to the decrease in the permeability of the membrane used for the research. The search for an appropriate interpretation of the phenomena was carried out using mathematical modeling. Based on the assumptions of the hydraulic model of the filtration resistance, calculations were made to forecast the efficiency of the osmotic membrane used in the discussed process. For this purpose, the following indicators were determined experimentally for the membrane: change in the volumetric flow of treated wastewater during low-pressure filtration, total hydraulic resistance, and component resistances, i.e., the resistance of the “new” membrane and resistances resulting from the reversible and irreversible fouling phenomena. It has been observed that irreversible resistance arises in the short and early stages of the process. The efficiency is determined by reversible resistance, which is confirmed by the literature.

A rapid, sensitive, economically and ecologically friendly method based on one-step ultrasound-assisted emulsification microextraction (USAEME) and in situ derivatization followed by gas chromatography-mass spectrometry (GC-MS) for simultaneous determination of low molecular benzotriazoles (LMBTs) and benzotriazole-based ultraviolet filters (BUVs) was developed. The optimized method allow quantification of benzotriazole (BT), 4-methylbenzotriazole (4MBT), 5-methylbenzotriazole (5MBT); 5-chlorobenzotriazole (5ClBT), 2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzortriazole (UV326) and 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole (UV329) in municipal and industrial (dairy) wastewater. The method was validated using real influent and effluent wastewater and samples at various stages of the purification process. Obtained relative recoveries were between 77 and 137%, limits of detection (LoDs) from 0.001 to 0.035 µg/L, the repeatability expressed by the coefficient of variation (CV) did not exceed 12%. The use of the method for the determination of the tested compounds in municipal and industrial wastewater showed their presence in most of the tested samples, in concentrations from LoD to 6.11 µg/L. The conducted studies of samples from municipal wastewater treatment plant (WWTP) located in north-eastern Poland showed that the effectiveness of benzotriazole removal by this plant is from 29 to 84%. The load of tested compounds released into the environment by this facility ranges from 2 to 269 mg/day/1000 inhabitants.

In recent years, there has been increasing interest in using of advanced oxidation processes in water and wastewater decontamination. As a new oxidants peracids, mainly peracetic acid (PAA) and peracid salts, i.e. peroxymonosulfate (PMS) and persulfate (PS) are used. The degradation process of organic compounds takes place with the participation of radicals, including hydroxyl (•OH) and sulfate (SO4•-) radicals derived from the peracids activation processes. Peracids can be activated in homogeneous systems (UV radiation, d-electron metal ions, e.g. Fe2+, Co2+, Mn2+, base, ozonolysis, thermolysis, radiolysis), or using heterogeneous activation (metals with zero oxidation state, metal oxides, quinones, activated carbon, semiconductors). As a result of oxidation, products of a lower mass than the parent compounds, less toxic, and more susceptible to biodegradation are formed. An important task is to investigate the effect of the peracid activation method and matrix composition on the efficiency of contamination removal. The article presents the latest information about the application of peracids in the removal of organic micropollutants of emerging concern (mainly focuses on endocrine disrupted compounds). The most important information on peracetic acid, peroxymonosulfate and persulfate salts, and methods of their activation are presented. Current uses of these oxidants in organic micropollutants removal are also described. Information was collected on the factors influencing the oxidation process and the effectiveness of pollutant removal. This paper compares PAA, PMS and PS-based processes for the first time in terms of kinetics and efficiency.

Benzotriazole UV stabilizers (BUVs) have gained popularity, due to their absorption properties in the near UV range (200–400 nm). They are used in the technology for manufacturing plastics, protective coatings, and cosmetics, to protect against the destructive influence of UV radiation. These compounds are highly resistant to biological and chemical degradation. As a result of insufficient treatment by sewage treatment plants, they accumulate in the environment and in the tissues of living organisms. BUVs have adverse effects on living organisms. This work presents the use of peracetic acid in combination with d-electron metal ions (Fe2+, Co2+), for the chemical oxidation of five UV filters from the benzotriazole group: 2-(2-hydroxy-5-methylphenyl)benzotriazole (UV-P), 2-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)-4-methylphenol (UV-326), 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol (UV-327), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (UV-328), and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (UV-329). The oxidation procedure has been optimized based on the design of experiments (DoE) methodology. The oxidation of benzotriazoles follows first order kinetics. The oxidation products of each benzotriazole were investigated, and the oxidation mechanisms of the tested compounds were proposed.

Phytohormones, such as auxins and cytokinins, take part in the integration of growth control and stress response, but their role in algal adaptation to heavy metal remains to be elucidated. The current research indicated that lead (Pb), one of the most toxic metals in nature, causes severe depletion of endogenous cytokinins, auxins, and gibberellin and an increase in abscisic acid content in the green alga Acutodesmus obliquus. Exogenous auxins and cytokinins alleviate Pb toxicity through the regulation of the endogenous phytohormones’ levels. Exogenously applied auxins provoked the coordinated activation metal tolerance mechanisms leading to the increase in phytochelatin synthase activity and accumulation of phytochelatins and their precursors, which are essential for Pb sequestration. On the other hand, phytochelatin synthesis decreased in algal cells treated with cytokinins. Significant changes in the levels of low molecular weight metabolites, mainly involved in metal chelation and glutathione synthesis pathway under the influence of phytohormones in algal cells growing in the presence of Pb stress, were observed. This is the first report showing that auxins and cytokinins are important regulatory factors in algal adaptation strategies to heavy metal stress based on thiol-mediated compounds and the maintenance of phytohormone homeostasis.

Phthalates or phthalic acid esters (PAEs) are chemical compounds whose use is exceptionally widespread in everyday materials but, at the same time, have been proven to have harmful effects on living organisms. Effluents from municipal wastewater treatment plants (WWTP) and leachates from municipal solid waste (MSW) landfills are important sources of phthalates with respect to naturally occurring waters. The main aim of this research was determination, mass loads, removal rates and ecological risk assessment of eight phthalates in municipal wastewaters, landfill leachates and groundwater from Polish WWTPs and MSW landfills. Solid-phase microextraction and gas chromatography with mass spectrometry were used for the extraction and determination of analytes. Summed up concentrations of eight phthalates ranged from below LOD to 596 μg/L in influent wastewater with the highest concentration found for bis-2-ethylhexyl phthalate (DEHP) (143 μg/L). The average degree of phthalate removal varies depending on the capacity of a given treatment plant with larger treatment plants coping better than smaller ones. The highest treatment efficiency for all tested treatment plants, over 90%, was reported for dimethyl phthalate (DMP) and diethyl phthalate (DEP). Overall concentrations of phthalates in leachates ranged from below LOD to 303 μg/L while the highest maximum concentration was registered for DEHP (249 μg/L). Overall concentrations of phthalic acid esters in groundwater from upstream monitoring wells ranged from below LOD to 1.8 μg/L and from LOD to 27.9 μg/L in samples from wells downstream of MSW landfills. The obtained data shows that diisobutyl phthalate (DIBP), dibutyl phthalate (DBP), DEHP, and diisononyl phthalate (DINP) pose a high risk for all trophic levels being considered in effluent wastewaters. In the case of groundwater high environmental risk was recorded for DBP and DEHP for all tested trophic levels. Phthalates, in concentrations that pose a high environmental risk, are present in Polish municipal after-treatment wastewater as well as in groundwater under municipal solid waste landfills.

The effects of auxins and cytokinins at the range of concentrations 0.0001–100 µM on Acutodesmus obliquus (Chlorophyceae) cultures were studied. Microalga exhibited sensitivity to cytokinins in the following order: 0.01 µM tZ > 0.1 µM Kin > 1 µM DPU, whereas the hierarchy of auxin activity was: 0.01 µM IAA > 0.1 µM IBA > 0.1 µM PAA. Cytokinins possessed higher stimulating properties on the cell number, whereas auxins increased the size of cells. Differences in the metabolite profiles of the cultures treated with phytohormones were observed. Auxins and cytokinins had a positive effect on the photosynthetic apparatus enhancing the level of chlorophylls, carotenes, and xanthophylls. In comparison with auxins, cytokinins more effectively delayed oxidative damage by increasing the level of non-enzymatic antioxidants (ascorbate, glutathione) and the activity of enzymes scavenging reactive oxidative species (catalase, glutathione reductase, ascorbate peroxidase). On the other hand, auxins stimulated superoxide dismutase activity and provoked hydrogen peroxide generation, which may be involved in cell enlargement. All phytohormones reduced the content of abscisic acid and controlled the level of endogenous auxin and cytokinins suggesting complex interactions. Different dynamics of A. obliquus responses to auxins and cytokinins clearly demonstrated their diverse roles in algal growth and metabolism.

A comprehensive study is presented, on the occurrence, removal, mass loading, and environmental risk assessment of 19 multi-class emerging organic contaminants in three Municipal Solid Waste landfills and three Wastewater Treatment Plants located at northeast Poland. The target compounds: methylparaben, ethylparaben, propylparaben, buthylparaben, benzophenone, benzophenone-2, benzophenone-3, 3-(4-methylbenzylidene) camphor, N,N-diethyltoluamide, 4-n-octylphenol, 4-n-nonylphenol, triclosan, bisphenol A, diclofenac, clotrimazole, carbamazepine, estrone, 17β-estradiol, diethylstilbestrol were in a wide range of concentration, from below limit of detection to 116 micrograms per liter in leachates and to 18 micrograms per liter in groundwaters and wastewaters. Benzophenone and bisphenol A were found in all analyzed samples. The highest total content of target chemical classes were registered for pharmaceuticals and phenols, 44% and 41%, respectively. Benzophenone-2 and diethylstilbestrol were not detected in all examined samples. In this study, mass loading of target analytes to aquatic ecosystem was calculated. Finally, environmental risk assessment has been presented as the risk quotient for effluent wastewaters and groundwaters on three trophic levels. Diclofenac was found to be the most critical compound in respect of environmental risk.

Textile effluent containing azo dyes such as C.I. Acid Violet 1 (AV1) can be degraded to toxic aromatic amines in the environment. Thus, there is a legitimate need to treat such effluents before they are discharged to surface waters. Two methods were proposed to remove AV1 from aqueous solutions: adsorption and advanced oxidation processes (AOPs). The sorption capacity of the strongly basic anion exchanger Purolite A520E of the polystyrene matrix determined from the Langmuir isotherm model was found to be 835 mg/g, while that of Lewatit S5428 of the polyacrylamide matrix Freundlich model seems to be more appropriate for describing the experimental data. The pseudo-second-order kinetic model and external diffusion are the rate limiting steps of adsorption. The removal efficiency of AV1 by the anion exchangers was higher than 99% after 40 min of phase contact time. AOPs involved the usage of hydrogen peroxide and peracetic acid (PAA) as oxidizing agents, while Fe2+ and simulated sunlight were used as oxidizing activators. AV1 oxidation followed the pseudo-first-order kinetics, and the systems with the highest values of the rate constants turned out to be those in which Fe2+ was present. The efficiency of oxidation measured by the degree of decolorization in the systems with Fe2+ was higher than 99% after 10–60 min. AV1 mineralization was slower, but after 120 min of oxidation it was higher than 98% in the H2O2/Fe2+, PAA/Fe2+ and PAA/Fe2+/sunlight systems.

The characteristics of the removal processes of the popular textile dye C.I. Acid Red 18 (AR18) using floating plants and anion-exchange resins are presented. The use of widespread floating plants Wolffia arrhiza, Lemna minor, Spirodela polyrhiza, and Azolla caroliniana was examined. Abiotic and biological mechanisms have been identified that are important in the removal of AR18 by plants. It has been shown that only two mechanisms are responsible for the removal of AR18 from aqueous solutions: plant uptake and plant sorption. The rate constants of these processes reach 0.099 d−1 and 0.130 d−1, respectively. The most effective dye removal was registered during experiments conducting with W. arrhiza, with an efficiency of 62% on average. In the adsorption process, the weakly basic anion exchanger Amberlyst A23 (A23) and non-functinalized resin Amberlite XAD761 (XAD761) of phenol-formaldehyde matrices were used. The sorption capacities of A23 and XAD761 determined from the Langmuir isotherm model were calculated as 329.1 mg/g (r2 = 0.999) and 22.3 mg/g (r2 = 0.998), respectively. The auxiliaries presence such as 0.5–2 g/L CH3COOH, 5–25 g/L Na2SO4, 0.1–0.5 g/L anionic or non-ionic surfactants in 500 mg/L AR18 solution do not reduce AR18 uptake by A23. Kinetic data of adsorption follows pseudo-second order equation rather than pseudo-first and intraparticle diffusion ones. The working ion exchange capacity (108.3 mg/mL) determined in the AR18-A23 column system confirmed a successful application of the weakly basic anion exchanger in purification adsorption step.

The development of civilization entails a growing demand for consumer goods. A side effect of the production and use of these materials is the production of solid waste and wastewater. Municipal and industrial wastewater usually contain a large amount of various organic compounds and are the main source of pollution of the aquatic environment with these substances. Therefore, the search for effective methods of wastewater and other polluted water treatment is an important element of caring for the natural environment. This Special Issue contains nine peer-review articles presenting research on the determination and removal of environmentally hazardous organic compounds from aqueous samples. The presented articles were categorized into three major fields: new approaches to the degradation of water pollutants, new methods of isolation and determination of the emerging organic contaminants (EOCs), and the occurrence of EOCs in the water environment. These articles present only selected issues from a very wide area, which is the removal of organic pollution in water environment, but can serve as important references for future studies.

The presented work is aimed to synthesize a new UV active derivative of α-lipoic acid (ALA) by its esterification with 4-methoxybenzyl alcohol (4-MBA, anise alcohol). The formation of ester was confirmed by 1HNMR, FTIR and UV spectroscopy. The analytical usefulness of the obtained compound for quantification of ALA in food items was examined using HPLC-UV and GC–MS systems. It was found that it is possible to assay ALA in the ester form in the concentration ranges: 5·10−6–1·10−4 mol L−1 by HPLC-UV and 1∙10−7–5∙10−5 mol L−1 by GC–MS techniques. The GC–MS procedure was applied for the determination of ALA in the food samples.

Heavy metals polluting the 100-year-old waste heap in Bolesław (Poland) are acting as a natural selection factor and may contribute to adaptations of organisms living in this area, including Trifolium repens and its root nodule microsymbionts—rhizobia. Exopolysaccharides (EPS), exuded extracellularly and associated with bacterial cell walls, possess variable structures depending on environmental conditions, they can bind metals and are involved in biofilm formation. In order to examine the effects of long-term exposure to metal pollution on EPS structure and biofilm formation of rhizobia, Rhizobium leguminosarum bv. trifolii strains originating from the waste heap area and a non-polluted reference site were investigated for the characteristics of the sugar fraction of their EPS using gas chromatography mass-spectrometry and also for biofilm formation and structural characteristics using confocal laser scanning microscopy under control conditions as well as when exposed to toxic concentrations of zinc, lead, and cadmium. Significant differences in EPS structure, biofilm thickness, and ratio of living/dead bacteria in the biofilm were found between strains originating from the waste heap and from the reference site, both without exposure to metals and under metal exposure. Received results indicate that studied rhizobia can be assumed as potentially useful in remediation processes.

Determination of the endocrine disrupting compounds (EDCs) in leachate and groundwater samples from the landfill sites is very important because of the proven harmful effects of these compounds on human and animal organisms. A method combining ultrasound-assisted emulsification microextraction (USAEME) and gas chromatography-mass spectrometry (GC-MS) was developed for simultaneous determination of seven personal care products (PCPs): methylparaben (MP), ethylparaben (EP), propylparaben (PP), buthylparaben (BP), benzophenone (BPh), 3-(4-methylbenzylidene)camphor (4-MBC), N,N-diethyltoluamide (DEET), and two hormones: estrone (E1) and β-estradiol (E2) in landfill leachate and groundwater samples. The limit of detection (LOD)/limit of quantification (LOQ) values in landfill leachate and groundwater samples were in the range of 0.003-0.083/0.009-0.277 μg L(-1) and 0.001-0.015/0.002-0.049 μg L(-1), respectively. Quantitative recoveries and satisfactory precision were obtained. All studied compounds were found in the landfill leachates from Polish municipal solid waste (MSW) landfills; the concentrations were between 0.66 and 202.42 μg L(-1). The concentration of pollutants in groundwater samples was generally below 0.1 μg L(-1).

Oilseed rape plants responded to water and salt stresses (-0.5 MPa, PEG 6000 and NaCI) by reduction of the fresh and dry weights of shoots and roots. When PEG was used, the ratio of dry weights of roots:shoots surpassed that of controls. The leaf protein content increased considerably. The phosphorus content decreased only in the roots, most significantly after three days of stress. Immediately after the stresses were induced, an increase in the acid phosphatase (AP) activity was noted. Water and salt stresses caused four- and two-fold increases in AP activity in leaves, respectively. Changes in the enzyme activity were negligible in stems and roots. There are nine forms of AP in young leaves of oilseed rape. In the stressed plants, from No. 5 revealed lower activity and forms Nos 8 and 9, higher activities than in the control. The increase in AP activity was directly accompanied by the decrease in the water potential of the tissues. Oilseed rape is considerably less sensitive to salt stress than to water stress, which is manifested as the lower inhibition of plant growth and also by a smaller increase in acid phosphatase activity.

The development of civilization entails a growing demand for consumer goods. A side effect of the production and use of these materials is the production of solid waste and wastewater. Municipal and industrial wastewater usually contain a large amount of various organic compounds and are the main source of pollution of the aquatic environment with these substances. Therefore, the search for effective methods of wastewater and other polluted water treatment is an important element of caring for the natural environment. This Special Issue contains nine peer-review articles presenting research on the determination and removal of environmentally hazardous organic compounds from aqueous samples. The presented articles were categorized into three major fields: new approaches to the degradation of water pollutants, new methods of isolation and determination of the emerging organic contaminants (EOCs), and the occurrence of EOCs in the water environment. These articles present only selected issues from a very wide area, which is the removal of organic pollution in water environment, but can serve as important references for future studies.

Ultrasound-assisted emulsification microextraction with solidification of floating organic droplet (USAEME-SFOD) has been applied to isolate hormones and other emerging contaminants from groundwater samples. Simultaneously with the extraction process, derivatization in the matrix was carried out using acetic anhydride. Quantification of studied organic pollutants was done through gas chromatography mass spectrometry (GC-MS). Hormones included &beta, estradiol (E2), estrone (E1), and diethylstilbestrol (DES). Other compounds belonged to groups of pharmaceuticals (diclofenac (DIC)), antiseptics (triclosan (TRC)), preservatives (propylparaben (PP) and butylparaben (BP)), sunscreen agents (benzophenone (BPH), and 3-(4-methylbenzylidene)camphor (3MBC)), repellents (N,N-diethyltoluamide (DEET)), industrial chemicals (bisphenol A (BPA), 4-t-octylphenol (4OP), 4-n-nonylphenol (4NP)). A non-toxic and inexpensive 1-undecanol was successfully used as the extraction solvent. Volume of extractant and derivatization agent, ionic strength, and time of extraction were optimized. Very low limits of detection (LoD) ranging from 0.01 to 5.9 ng/L were obtained. Recoveries ranged from 90% to 123%, with relative standard deviation being lower than 17%. The developed procedure was used to determine target compounds in groundwater collected at municipal waste landfills as well as in groundwater from wells distant from sources of pollution.

Direct immersion solid-phase microextraction has been optimized and applied to the simultaneous determination of the neutral and basic pharmaceuticals: caffeine, carbamazepine, clomipramine, chlorprothixene and clotrimazole at low concentrations in municipal wastewater. Two absorption type stationary phases: polydimethylsiloxane (PDMS) and polyacrylate (PA) have been found to be most effective for extraction of target analytes. The separation and detection were carried out by gas chromatograph coupled with mass spectrometer working in the selected ion monitoring mode. The method was validated for linearity, detection and quantitation limits, selectivity and precision. The average correlation coefficient of the calibration curves was 0.9933. The LOD values in influent and effluent wastewater were in the range of 10–145 ng L−1 and 4–111 ng L−1, respectively, which were a bit higher than those in the deionized water due to matrix effect. The high values of distribution coefficient (K fs ) in PDMS/water and PA/water systems (log K fs between 3.05 and 4.23) indicates the very high applicability of these stationary phases for determination of carbamazepine, clomipramine, chlorprothixene and clotrimazole in water samples.

The ether and methanol extracts of Wolffia arrhiza (Lemnaceae) were analyzed using high resolution capillary gas chromatography coupled with mass spectrometry (GC-MS). The ether extract contains 32 compounds, mostly lipids and sterols, among which β-sitosterol is most prevalent. This is the first evidence of β-sitosterol detection in W. arrhiza. The most representative group of polar compounds of the methanol fraction is formed by 18 free amino acids. In addition, in the methanol extract there are a number of other nitrogen containing compounds: nucleobase and nucleosides. The third significant group in the total ion current in the methanol extract is formed by glycerol and glycerides. At the same time, the content of free sugar is very low.

The first-order kinetic reaction rate model is used in predicting the leaching of atrazine and inorganic compounds (\( {\mathrm{K}}^{+1} \), \( {\mathrm{Fe}}^{+3} \), \( {\mathrm{Mg}}^{+2} \), \( {\mathrm{Mn}}^{+2} \), \( {\mathrm{NH}}_4^{+} \), \( {\mathrm{NO}}_3^{-} \), and \( {\mathrm{PO}}_4^{-3} \)) from tilled and orchard silty loam soils. This model provided an excellent fit to the experimental concentration changes of the compounds vs. time data during leaching. Calculated values of the first-order reaction rate constants for the changes of all chemicals ranged from 3.8 to 19.0 times higher in orchard than in tilled soil. Higher first-order reaction constants for orchard than tilled soil are in line with both higher total porosity and contribution of biological pores in the former. The first-order reaction constants for the leaching of chemical compounds enable the prediction of the actual compound concentration and the interactions between compound and soil as affected by management system. The study demonstrates the effectiveness of simultaneous chemical and physical analyses as a tool for the understanding of leaching in variously managed soils.

The present study discusses the influence of sunlight on the photostability of levomepromazine (LV) and olanzapine (OLA) hydrochlorides in river water. Four samples of water from different rivers were used in the research. In their course, it turned out that levomepromazine easily underwent photooxidation under simulated environmental conditions, resulting in the generation of its sulphoxide. Olanzapine, on the other hand, appeared to be more resistant to sunlight, as its photodecomposition proceeded slowly, and only one product of its decomposition was detected spectrophotometrically during the process. The photodegradation was analyzed in detail using principal component analysis (PCA) and multivariate curve resolution alternating least squares (MCR-ALS) chemometric methods, and the outcomes verified by HPLC and GC-MS analysis. It can be stated that the rates of the observed processes heavily depended on the chemical composition of the fresh water used in the experiments.

To clarify the differences in physical aspects (water permeability and macropore) between organically (OR) and conventionally managed (CO) soils, infiltration was measured at an experimental field managed in Pulawy, Poland. Soil columns at depths of 0–20 cm (diameter 21.5 cm) were also collected from the field to determine infiltration and flow–active porosity (macropore). The infiltration rate was 6–10 times higher in OR than in CO, owing to larger macropores in OR. The larger macropores in OR could presumably be due to two factors: (1) the fact that compost and clover (Trifolium repens)–grass were applied only to the organically managed field; (2) the larger population of earthworms (Eisenia foetida) in the organically managed field, which prefer applied organic matter and dislike agrochemicals. These findings, of the higher infiltration and the larger macropore in OR than in CO, may demonstrate one positive effect of organic soil management.

Liquid-liquid partition is used in sample preparation and in countercurrent and liquid-liquid chromatographic separations. Partition coefficients are widely used in toxicology, environmental, and analytical chemistry. The K hn determination procedure for the n-hexane/nitromethane system was optimized and partition coefficients for 99 ketones, esters and trimethylsilyl derivatives of phenols, aliphatic and aromatic acids were determined. For 130 compounds, K hn values were predicted using mathematical relationships between K hn and other physicochemical and structural parameters.

The aim of the research involved identification and semi-quantitative determination of unknown volatile and semi-volatile organic compounds emitted to air by sewage sludge formed in the process of municipal wastewater treatment in a sewage treatment plant. Samples taken directly after completion of the technological process as well as the sludge stored on the premise of the sewage treatment plant were analyzed. A simple method using off-line headspace solid-phase microextraction combined with gas chromatography-mass spectrometry has been proposed for extraction and detection of organic pollutants. For reliable identification of compounds, combination of two independent parameters: mass spectra and linear temperature programmed retention indices were employed. Over 170 compounds of different structure were identified including aliphatic and aromatic hydrocarbons, alcohols, esters, carbonyls, as well as sulfur, nitrogen, and chlorine containing compounds. The prevailing substances included: ethyl ether, n-hexane, p-xylene, o-xylene, mesitylene, m-ethylbenzene, limonene, n-decane, n-undecane, and n-dodecane. A few compounds such as methanetiol, dimethyl polisulfide, octaatomic sulfur, phthalic anhydride, and indoles were identified in the sludge for the first time.

The aim of this study was to examine the leaching of potassium, magnesium, manganese and iron in tilled and orchard silty loam soil. The experimental treatments were: conventionally tilled field (CT) with main tillage operations including pre-plough (10 cm)+harrowing followed by mouldboard ploughing to 20 cm depth, and a 35-year-old apple orchard (OR) with a permanent sward. Leaching of the cations was determined in soil columns of undisturbed structure, 21.5 cm diameter and 20 cm height, from a depth of 0–20 cm. All the columns were subjected to spray irrigation at a level of 1110 ml (30 mm), and leachate in 50-ml increments was collected. Concentration of the cations in the leachate was determined using a spectrophotometer ICP-AS. Pore size distribution data showed that the volume of pores >20 µm under CT was greater at a depth of 0–10 cm and lower in the 10–20 cm soil layer under OR, and the reverse was true with respect to pores

Solid-phase microextraction (SPME) employing absorption type fibers coupled to gas chromatography was used to extract phthalic acid esters from water samples. Distribution coefficients between water and polydimethylsiloxane ( K fw PDMS ) and polyacrylate ( K fw PA ) for these compounds were determined. To estimate the values of Kfw for compounds of the same class, which did not undergo experiments, it is proposed to use an empirical two-parameter equation in which various physico-chemical and structural characteristics weakly correlated with each other are used as descriptors. Kfw values calculated on the basis of correlation with distribution coefficients in other heterogeneous systems correspond to the values determined experimentally. Distribution coefficients in polyacrylate/water system were used for quantitative determination by SPME–GC–FID method of phthalates in raw and purified municipal wastes which come from a wastewater purifying plant in Bialystok. Concentration of the four phthalates detected in the wastewater (di-n-propyl phthalate, diisobutyl phthalate, di-n-butyl phthalate and di-2-ethylhexyl phthalate) ranged from 1.5 to 50 μg/l. During a purification process, decomposition of phthalates with higher polarity is the fastest whereas that of di-2-ethylhexyl phthalate is the slowest.

Atrazine is the most commonly detected herbicide in the groundwater. Leaching of atrazine largely depends on soil management practices. The aim of this study was to examine leaching of atrazine in tilled and orchard silty loam soils. The experimental objects included: conventionally tilled field (CT) with main tillage operations including pre-plow (10 cm)+harrowing, mouldboard ploughing (20 cm), and a 35 year-old apple orchard (OR) with a permanent sward. To determine leaching of atrazine soil columns of undisturbed structure were taken with steel cylinders of 21.5 cm diameter and 20 cm high from the depth of 0-20 cm. All columns were equilibrated at water content corresponding to field capacity (0.21 kg kg(-1)). Atrazine suspended in distilled water was dripped uniformly onto the surface of each column. Then water was infiltrated and breakthrough times of leachates were recorded. Atrazine concentration in the leachates was determined by means of HPLC Waters. Macro-porosity and percolation rate were higher in OR than CT soil. Cumulative recovery % of the atrazine applied was 1.267% for OR and approximately one third more from the CT soil but the rate of leaching (per unit of time) was greater from the OR soil. The lower leaching under OR than CT can be due to a greater SOM and the presence of earthworm burrows with organic burrow linings that could adsorb atrazine and contribute to preferential flow allowing solutes to bypass parts whereas the greater rate of leaching due to a greater infiltration rate. The results indicate potential of management practices for minimizing atrazine leaching.

This paper reports the experimentally determined and calculated partition coefficients (Kp) in a heterogeneous system consisting of two partially mixing organic solvents for trimethylsilyl derivatives of 119 compounds including phenols, phenolcarboxylic acids, mono- and dicarboxylic acids, and some carbohydrates and polyols. It was demonstrated that a simple model based on the available physico-chemical properties of molecules can be used to accurately predict the hexane-acetonitrile partition coefficients. Phenols, other organic acids, and carbohydrates form complex mixtures in extracts of plant tissues, in various biological fluids, as well as in waste waters. For group identification of these mixture components, it is desirable to use the parameterj which is a combination of Kp and gas chromatographic retention indices: j = kI - log Kp. This approach increases identification reliability in gas chromatographic analysis. The use of the group parameterj in the analysis of nonvolatile organic components of waste waters is reported.

Research results of mechanically-dehydrated sewage sludge utilisation in cement kiln are presented. The fuel mix was obtained by mixing sewage sludge with fuel oil and waste oil. Non-ionic surfactants Rokafenol N8 and Rokacet S7 were used as emulsifier. Technical tests of utilisation of sewage sludge (supplied to a cement kiln with clinker slurry) and combustion of its mixtures with fuel oil were run at the Rejowiec Cement Works. It was found that the utilisation of sewage sludge in cement kilns does not cause any excess harassment to the environment.

A method combining ultrasound-assisted emulsification-microextraction (USAEME) with gas chromatography-mass spectrometry (GC-MS) was developed for simultaneous determination of four acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, and diclofenac, as well as four phenols, 4-octylphenol, 4-n-nonylphenol, bisphenol A, and triclosan in municipal wastewaters. Conditions of extraction and simultaneous derivatization were optimized with respect to such aspects as type and volume of extraction solvent, volume of derivatization reagent, kind and amount of buffering salt, location of the test tube in the ultrasonic bath, and extraction time. The average correlation coefficient of the calibration curves was 0.9946. The LOD/(LOQ) values in influent and effluent wastewater were in the range of 0.002-0.121/(0.005-0.403) μg L(-1) and 0.002-0.828/(0.006-2.758) μg L(-1), respectively. Quantitative recoveries (≥94%) and satisfactory precision (average RSD 8.2%) were obtained. The optimized USAEME/GC-MS method was applied for determination of the considered pharmaceuticals and phenols in influents and treated effluents from nine Polish municipal wastewater treatment plants. The average concentration of acidic pharmaceuticals in influent and effluent wastewater were in the range of 0.06-551.96 μg L(-1) and 0.01-22.61 μg L(-1), respectively, while for phenols were in the range of 0.03-102.54 μg L(-1) and 0.02-10.84 μg L(-1), respectively. The removal efficiencies of the target compounds during purification process were between 84 and 99%.