Environmental Analytical Chemistry.

Environmental analytical chemistry has evolved into a well-established interdisciplinary field (analytical chemistry, pollution chemistry, chemical engineering, etc [...].

Langmuir-Blodgett Films with Immobilized Glucose Oxidase Enzyme Molecules for Acoustic Glucose Sensor Application.

In this work, a sensitive coating based on Langmuir-Blodgett (LB) films containing monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) with an immobilized glucose oxidase (GOx) enzyme was created. The immobilization of the enzyme in the LB film occurred during the formation of the monolayer. The effect of the immobilization of GOx enzyme molecules on the surface properties of a Langmuir DPPE monolayer was investigated. The sensory properties of the resulting LB DPPE film with an immobilized GOx enzyme in a glucose solution of various concentrations were studied. It has shown that the immobilization of GOx enzyme molecules into the LB DPPE film leads to a rising LB film conductivity with an increasing glucose concentration. Such an effect made it possible to conclude that acoustic methods can be used to determine the concentration of glucose molecules in an aqueous solution. It was found that for an aqueous glucose solution in the concentration range from 0 to 0.8 mg/mL the phase response of the acoustic mode at a frequency of 42.7 MHz has a linear form, and its maximum change is 55°. The maximum change in the insertion loss for this mode was 18 dB for a glucose concentration in the working solution of 0.4 mg/mL. The range of glucose concentrations measured using this method, from 0 to 0.9 mg/mL, corresponds to the corresponding range in the blood. The possibility of changing the conductivity range of a glucose solution depending on the concentration of the GOx enzyme in the LB film will make it possible to develop glucose sensors for higher concentrations. Such technological sensors would be in demand in the food and pharmaceutical industries. The developed technology can become the basis for creating a new generation of acoustoelectronic biosensors in the case of using other enzymatic reactions.

Langmuir-Blodgett Films of Arachidic and Stearic Acids as Sensitive Coatings for Chloroform HF SAW Sensors.

Properties of the Langmuir-Blodgett (LB) films of arachidic and stearic acids, versus the amount of the films' monolayers were studied and applied for chloroform vapor detection with acoustoelectric high-frequency SAW sensors, based on an AT quartz two-port Rayleigh type SAW resonator (414 MHz) and ST-X quartz SAW delay line (157.5 MHz). Using both devices, it was confirmed that the film with 17 monolayers of stearic acid deposited on the surface of the SAW delay line at a surface pressure of 30 mN/m in the solid phase has the best sensitivity towards chloroform vapors, compared with the same films with other numbers of monolayers. For the SAW resonator sensing using slightly longer arachidic acid molecules, the optimum performance was reached with 17 LB film layers due to a sharper decrease in the Q-factor with mass loading. To understand the background of the result, Atomic Force Microscopy (AFM) in intermittent contact mode was used to study the morphology of the films, depending on the number of monolayers. The presence of the advanced morphology of the film surface with a maximal average roughness (9.3 nm) and surface area (29.7 µm2) was found only for 17-monolayer film. The effects of the chloroform vapors on the amplitude and the phase of the acoustic signal for both SAW devices at 20 °C were measured and compared with those for toluene and ethanol vapors; the largest responses were detected for chloroform vapor. For the film with an optimal number of monolayers, the largest amplitude response was measured for the resonator-based device. Conversely, the largest change in the acoustic phase produced by chloroform adsorption was measured for delay-line configuration. Finally, it was established that the gas responses for both devices coated with the LB films are completely restored 60 s after chamber cleaning with dry air.

Sediment Assessment of the Pchelina Reservoir, Bulgaria.

The temporal dynamics of anthropogenic impacts on the Pchelina Reservoir is assessed based on chemical element analysis of three sediment cores at a depth of about 100-130 cm below the surface water. The 137Cs activity is measured to identify the layers corresponding to the 1986 Chernobyl accident. The obtained dating of sediment cores gives an average sedimentation rate of 0.44 cm/year in the Pchelina Reservoir. The elements' depth profiles (Ti, Mn, Fe, Zn, Cr, Ni, Cu, Mo, Sn, Sb, Pb, Co, Cd, Ce, Tl, Bi, Gd, La, Th and Unat) outline the Struma River as the main anthropogenic source for Pchelina Reservoir sediments. The principal component analysis reveals two groups of chemical elements connected with the anthropogenic impacts. The first group of chemical elements (Mn, Fe, Cr, Ni, Cu, Mo, Sn, Sb and Co) has increasing time trends in the Struma sediment core and no trend or decreasing ones at the Pchelina sampling core. The behavior of these elements is determined by the change of the profile of the industry in the Pernik town during the 1990s. The second group of elements (Zn, Pb, Cd, Bi and Unat) has increasing time trends in Struma and Pchelina sediment cores. The increased concentrations of these elements during the whole investigated period have led to moderate enrichments for Pb and Unat, and significant enrichments for Zn and Cd at the Pchelina sampling site. The moderately contaminated, according to the geoaccumulation indexes, Pchelina Reservoir surface sediment samples have low ecotoxicity.

Chemometric Assessment of Bulgarian Wastewater Treatment Plants' Effluents.

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

Assessment of the Bulgarian Wastewater Treatment Plants' Impact on the Receiving Water Bodies.

Deterioration of water quality is a major problem world widely according to many international non-governmental organizations (NGO). As one of the European Union (EU) countries, Bulgaria is also obliged by EU legislation to maintain best practices in assessing surface water quality and the efficiency of wastewater treatment processes. For these reasons studies were undertaken to utilize ecotoxicological (Microtox®, Phytotoxkit FTM, Daphtoxkit FTM), instrumental (to determine pH, electrical conductivity (EC), chemical oxygen demand, total suspended solids (TSS), total nitrogen (N) and phosphorus (P), chlorides, sulphates, Cr, Co, Cu, Cd, Ba, V, Mn, Fe, Ni, Zn, Se, Pb), as well as advanced chemometric methods (partial least squares-discriminant analysis (PLS-DA)) in data evaluation to comprehensively assess wastewater treatment plants' (WWTPs) effluents and surface waters quality around 21 major Bulgarian cities. The PLS-DA classification model for the physicochemical parameters gave excellent discrimination between WWTP effluents and surface waters with 93.65% correct predictions (with significant contribution of EC, TSS, P, N, Cl, Fe, Zn, and Se). The classification model based on ecotoxicological data identifies the plant test endpoints as having a greater impact on the classification model efficiency than bacterial, or crustaceans' endpoints studied.

Bioaccessibility of Cd, Cu, Fe, Mn, Pb, and Zn in hazelnut and walnut kernels investigated by an enzymolysis approach.

Bioaccessibility of four essential (Fe, Cu, Mn, Zn) and two toxic (Cd, Pb) elements in kernels of four walnut and four hazelnut cultivars was investigated using sequential enzymolysis approach and atomic absorption spectrometry. It was found that the assimilable part of elements was not dependent on nut cultivar. The bioaccessible fraction of Cu, Mn, and Zn was definitely higher for hazelnuts (62% Cu, 39% Mn, 58% Zn) than for walnuts (14% Cu, 21% Mn, 15% Zn). Bioaccessible Fe was 20-24% from its total content for both nut types. Solubility in the simulated intestinal juice is affected by both formation of stable soluble complexes and back sorption of dissolved elements on nut solid residues. Lead shows strong insolubility due to the high sorption affinity of lead ions to the insoluble fraction of nuts. Thus, walnuts and hazelnuts could act as effective biosorbents for lead detoxication.

Development of the first certified reference materials for several brominated flame retardants in polymers.

The first reference materials certified for several polybrominated flame retardants in polymers were developed. Commercially available polyethylene and polypropylene were fortified with technical mixtures of Pentabrominated diphenylether (Penta-BDE), Octa-BDE, Deca-BDE, and Decabrominated biphenyl (BB) (where the capitalized forms refer to the technical mixtures). Homogeneity was tested on 20 units of each material, and between-unit variation was confirmed to be below 4% for all congeners. Stability was assessed after storage of samples for 1 year at 4, 18, and 60 degrees C. Uncertainty of degradation during transport was found negligible for all congeners, whereas uncertainty of degradation for storage of 24 months at 4 degrees C was estimated between 2% and 11%. A characterization intercomparison involving 16 laboratories was organized. After exclusion of technically doubtful results, between-laboratory standard deviations ranged from 3% to 12%, making this intercomparison the best for this field of analysis so far. Statistical analysis revealed that the use of isotopically labeled internal standards did not improve analytical precision in this study. The good comparability, together with the independent confirmation of the assigned mass fractions via the total bromine content as well as by using non-GC/MS-based methods, allowed for the first time the certification of polymer materials for several brominated flame retardants.

Stable isotope pilot study of exchangeable copper kinetics in human blood plasma.

To develop further our understanding of initial dietary copper metabolism, a method has been developed to separate plasma copper that is bound to albumin, from that bound to ceruloplasmin. This method has been tested using plasma samples from a pilot study involving six human volunteers who consumed 3mg oral doses of the stable isotope (65)Cu and gave blood samples at timed intervals up to 7 days. The results suggest that this method can be used to monitor dynamic fluctuations in newly absorbed copper over a short time frame.

Properties of the copper(II)-histidine complex obtained after dialysis of human plasma with histidine.

The copper(II)-histidine complex obtained following dialysis of human plasma with histidine was investigated using various types of extraction systems and ion exchange resins. According to the results obtained, the Cu(II)-histidine complex formed under the dialysis conditions has one positive charge. Preconcentration of copper from the dialysis solution was achieved by its extraction as a dithiocarbamate complex and by sorption on cation-exchange resin or onto chelate sorbent.

Use of mathematical modeling to study copper metabolism in humans.

BACKGROUND: An improved understanding of copper metabolism is needed to derive more precise estimates of dietary requirements. OBJECTIVES: The objectives were to validate a method for estimating endogenous losses of copper, test whether a simple model can predict true absorption from the plasma appearance of labeled copper, and develop a compartmental model for copper metabolism by using stable isotopes. DESIGN: A stable isotope of copper was intravenously administered to 6 men, and fecal samples were collected for 14 d. Four weeks later the study was repeated, but with an oral dose, and blood samples were collected for 7 d and fecal samples for 14 d. RESULTS: There was no significant difference (P = 0.48) in the estimated endogenous loss of copper calculated by using either the excreted intravenous dose (x +/- SD: 32 +/- 5%) or the absorbed and excreted oral dose (35 +/- 2%). A simple mathematical model fitted to plasma isotope appearance data estimated true absorption to be 8 +/- 2% compared with 48-49% measured by fecal monitoring. A more complicated compartmental model predicted that, when newly absorbed copper first enters the blood, 74% is removed by the liver and 99% is bound to ceruloplasmin in the plasma. The exchangeable pool of copper was estimated to be 43 +/- 30 mg. Daily endogenous losses were predicted to be 2.4 mg. CONCLUSIONS: The results showed that fecal monitoring is the only method that can reliably measure labeled copper absorption, and it is not necessary to administer an intravenous dose of copper to estimate endogenous losses. The compartmental model provides new insights into human copper metabolism.

Dialysis-Chelex method for determination of exchangeable copper in human plasma.

A method based on dialysis in the presence of histidine, and subsequent copper adsorption and preconcentration using Chelex-100 resin, has been developed for selective extraction of exchangeable copper from blood plasma. The method was verified by comparative analysis using two different instrumental techniques, ICP-MS and AAS. The results obtained were in excellent agreement. Accurate quantification of the exchangeable copper and the firmly bound copper was achieved. The method was further validated by analysis of a lyophilised human serum certified reference material.