Migration of trace elements and radioisotopes to various fractions of solid wastes generated as a result of the sewage sludge incineration process.

The research was aimed at providing new knowledge in the field of chemical characteristics of solid waste generated in the process of combustion of sewage sludge in fluidized bed furnaces. The research material consisted of disposed fluidized beds (DFB), sewage sludge ash (SSA) and air pollution control residues (APC) from three Polish installations for the thermal treatment of sewage sludge. Natural radionuclides as well as anthropogenic isotope 137Cs were determined in the tested materials and the migration of a wide spectrum of trace elements to various waste fractions generated in the process of sewage sludge combustion was examined. It was observed that both radioisotopes and most of the trace elements determined accumulate in SSA and DFB, while the APC fraction contains a much smaller amount of them. The exceptions are mercury and selenium, whose volatile compounds migrate to the exhaust gas dedusting system and accumulate in the APC fraction (up to 40 mg/kg and 13 mg/kg, respectively). A potential threat from the 226Ra isotope in SSA is identified in the context of the management of this waste in the production of building materials because the typical activity of 226Ra in SSA collected from areas with very low Ra content in natural environment exceeds 1.5-6 times the activity of this isotope in conventional cement mixtures. When managing SSA and DFB, special attention should be paid to the content of metalloids such as As, B and Se, due to the high content of mobile forms of these elements in the mentioned materials.

Comparative Analysis of Laboratory-Made and Industrial-Made Sewage Sludge Ash: Implications for Effective Management Strategy Development.

In the pursuit of environmentally and economically sustainable sewage sludge ash (SSA) management methods, researchers often employ laboratory-made SSA (L-SSA) as a substitute for industrial-made SSA (I-SSA) produced in fluidized bed furnaces. To check whether L-SSA is a material that imitates I-SSA well, the fractionation of metals whose presence is a significant problem during SSA management was performed. In addition, the grain distribution, specific surface area, and textural properties of the tested materials were examined. Differences in total Pb and Hg content and mobility of Cu, Ni, Mn, and Zn were observed between I-SSA and L-SSA. Larger particle sizes of L-SSA compared to I-SSA were confirmed, while comparable textural properties and specific surface area of both types of materials were maintained. Based on the results, it was concluded that L-SSA is chemically different compared to I-SSA, and that L-SSA should not be used as a reference in research focused on the design of SSA management methods. Moreover, fractionation of metals was performed in disposed fluidized beds (FBs), which are diverted to non-hazardous waste landfills without prior analysis. It has been proven that studied metals are present in FBs as abundantly as in SSA, while Cu, Mn, and Ni may show higher mobility than in I-SSA.

Do You Know What You Drink? Comparative Research on the Contents of Radioisotopes and Heavy Metals in Different Types of Tea from Various Parts of the World.

The aim of this study was to assess the potential health risks of radioactive elements and heavy metals ingested through the consumption of various types of tea imported to the Polish market (black, green, red, oolong and white). The concentrations [Bq/kg] of radionuclides (40K, 137Cs, 226Ra, 210Pb and 228Th) in tea leaves before and after brewing were measured using γ-ray spectrometry with high-purity germanium (HPGe). The concentrations [mg/kg] of the studied elements (Fe, Cr, Cu, Mo, Al, Mn, Ni, P, V, Cd and Pb) were determined using a microwave-induced plasma optical emission spectrometer (MIP-OES). The results presented here will help to expand the database of heavy metals and radioactivity in teas. With regard to the potential health risk, the percentage of leaching of individual elements in different types of tea infusions was determined, and the assessment of the consumption risk was estimated. Since the calculated exposure factors, namely the HQ (Hazard Quotient) and THQ (Target Hazard Quotient), do not exceed critical levels, teas can still be considered health-beneficial products (most of the radionuclides as well as elements remain in the leaves (65-80%) after brewing).

Cytocompatibility, antibacterial, and corrosion properties of chitosan/polymethacrylates and chitosan/poly(4-vinylpyridine) smart coatings, electrophoretically deposited on nanosilver-decorated titania nanotubes.

The development of novel implants subjected to surface modification to achieve high osteointegration properties at simultaneous antimicrobial activity is a highly current problem. This study involved different surface treatments of titanium surface, mainly by electrochemical oxidation to produce a nanotubular oxide layer (TNTs), a subsequent electrochemical reduction of silver nitrate and decoration of a nanotubular surface with silver nanoparticles (AgNPs), and finally electrophoretic deposition (EPD) of a composite of chitosan (CS) and either polymethacrylate-based copolymer Eudragit E 100 (EE100) or poly(4-vinylpyridine) (P4VP) coating. The effects of each stage of this multi-step modification were examined in terms of morphology, roughness, wettability, corrosion resistance, coating-substrate adhesion, antibacterial properties, and osteoblast cell adhesion and proliferation. The results showed that the titanium surface formed nanotubes (inner diameter of 97 ± 12 nm, length of 342 ± 36 nm) subsequently covered with silver nanoparticles (with a diameter of 88 ± 8 nm). Further, the silver-decorated nanotubes were tightly coated with biopolymer films. Most of the applied modifications increased both the roughness and the surface contact angle of the samples. The deposition of biopolymer coatings resulted in reduced burst release of silver. The coated samples revealed potent antimicrobial activity against both Gram-positive and Gram-negative bacteria. Total elimination (99.9%) of E. coli was recorded for a sample with CS/P4VP coating. Cytotoxicity results using hFOB 1.19, a human osteoblast cell line, showed that after 3 days the tested modifications did not affect the cellular growth according to the titanium control. The proposed innovative multilayer antibacterial coatings can be successful for titanium implants as effective postoperative anti-inflammation protection.

Estimation of smokers' exposure to mercury from combustible tobacco products, based on the approach used in food consumers' exposure estimation.

Smoking has been known to mankind for centuries, but it is only in recent decades that much attention has been paid to the harmfulness of this habit. Mercury inhalation is particularly dangerous in this respect and smoking creates extremely favorable conditions for the emission and targeted delivery of this element into the lungs. Despite this fact, a lack of a clear method for estimating the exposure of tobacco consumers to mercury was identified. This work shows justification to transfer the approach of estimating food product consumers' exposure to estimate the exposure of combustible tobacco product consumers to this element. In addition, it was noted that researchers' attention is mainly focused on cigarettes, while the tobacco market has a wide range of combustible products. Therefore, in this work, the mercury content of cigars (8.45 ± 0.18-41.02 ± 0.20 µg/kg), pipe tobaccos (8.03 ± 0.52-25.48 ± 0.50 µg/kg), bidis (14.93 ± 0.47-31.79 ± 0.26 µg/kg) and cigarette tobaccos (14.22 ± 0.71-34.5 ± 1.4 µg/kg) was analyzed. This study demonstrates that smoking can contribute significant total mercury exposure to consumers', although it is unlikely to cause mercury poisoning regardless of other exposure sources.

Antibacterial properties of laser-encapsulated titanium oxide nanotubes decorated with nanosilver and covered with chitosan/Eudragit polymers.

To provide antibacterial properties, the titanium samples were subjected to electrochemical oxidation in the fluoride-containing diethylene glycol-based electrolyte to create a titanium oxide nanotubular surface. Afterward, the surface was covered by sputtering with silver 5 nm film, and the tops of the nanotubes were capped using laser treatment, resulting in an appearance of silver nanoparticles (AgNPs) of around 30 nm in diameter on such a modified surface. To ensure a controlled release of the bactericidal substance, the samples were additionally coated with a pH-sensitive chitosan/Eudragit 100 coating, also exhibiting bactericidal properties. The modified titanium samples were characterized using SEM, EDS, AFM, Raman, and XPS techniques. The wettability, corrosion properties, adhesion of the coating to the substrate, the release of AgNPs into solutions simulating body fluids at different pH, and antibacterial properties were further investigated. The obtained composite coatings were hydrophilic, adjacent to the surface, and corrosion-resistant. An increase in the amount of silver released as ions or metallic particles into a simulated body fluid solution at acidic pH was observed for modified samples with the biopolymer coating after three days of exposure avoiding burst effect. The proposed modification was effective against both Gram-positive and Gram-negative bacteria.

Review of cigars and cigar-type products as potential sources of consumer exposure to heavy metals.

The popularity of cigars, growing since 1993, has not gone hand in hand with the increased interest of researchers in these products. Although the literature widely describes the harmfulness of tobacco and the content of toxic substances in tobacco products, the topic is often treated selectively as relating primarily to cigarettes and rarely extends to other products of the broadly defined tobacco industry. However, there is no reason to marginalize the harmful effects of other nicotine products, (which include tobacco products such as cigars). The study analyzed the available literature on the content of selected heavy metals in cigar tobacco. Among the heavy metals, the following contents of elements in tobacco were recorded in cigars: Fe (420-2200 µg/g), Mn (100-370 µg/g), Zn (14-180 µg/g), Cu (15-140 µg/g), Pb (not detected-32 µg/g), Cd (nd-19 µg/g), Ni (nd-13 µg/g), Cr (nd-10 µg/g), Co (0.65-1.0 µg/g), As (nd-0.66 µg/g), Hg (18-25 ng/g). Importantly, the values often differ between cigars of different origins and types, indicating the need for more extensive research.

Influence of Cement Replacement with Sewage Sludge Ash (SSA) on the Heat of Hydration of Cement Mortar.

The amount of fly ash from the incineration of sewage sludge is increasing all over the world, and its utilization is becoming a serious environmental problem. In the study, a type of sewage sludge ash (SSA) collected directly from the municipal sewage treatment plant was used. Five levels of cement replacement (2.5%, 5%, 7.5%, 10% and 20%) and unchanged water-to-binder (w/b) ratio (0.55) were used. The purpose of the study was to evaluate the effect of sewage sludge ash (SSA) on the hydration heat process of cement mortars. The heat of the hydration of cement mortars was monitored by the isothermal calorimetric method for 7 days at 23 °C. The analysis of chemical composition and particle size distribution was performed on the tested material. The tests carried out have shown that SSA particles have irregular grain morphology and, taking into account the chemical composition consists mainly of oxides such as CaO, P2O5, SiO2 and Al2O3. The concentration of these compounds affects the hydration process of cement mortars doped with SSA. In turn, the content of selected heavy metals in the tested ash should not pose a threat to the environment. Calorimetric studies proved that the hydration process is influenced by the presence of SSA in cement mortars. The studies showed that the rate of heat generation decreased (especially in the initial setting period) with the increasing replacement of cement by SSA, which also reduced the amount of total heat compared to the control cement mortar. With increasing mass of the replacement of cement with SSA up to 20%, the 7-day compressive strength of the mortar samples decreases.

Accumulation of radioisotopes and heavy metals in selected species of mushrooms.

Seven species of forest mushrooms from different regions of Poland (edible: Imleria badia, Cantharellus cibarius, Xerocomus subtomentosus, Suillus luteus and inedible by humans but being food for animals: Paxillus involutus, Tylopilus felleus and Russula emetica) were analyzed for radioisotope activity (Cs-137, K-40, Bi-214 and Pb-210) as well as concentrations of heavy metals (aluminum, chromium, cadmium, manganese, iron, lead, zinc, copper, nickel and mercury). The activity of radioisotopes was measured with a gamma spectrometer, while the concentrations of heavy metals were examined by microwave plasma - atomic emission spectrometry. The obtained results of the analyses were compared with the recommendations of the European Food Safety Authority concerning the consumption of the determined heavy metals and the European standards concerning the content of radioisotopes in food. The obtained results proved that the consumption of mushrooms may result in a significant exceeding of the consumption limits of cadmium, copper and Cs-137.

Electrophoretically Deposited Chitosan/Eudragit E 100/AgNPs Composite Coatings on Titanium Substrate as a Silver Release System.

Due to the possibility of bacterial infections occurring around peri-implant tissues, it is necessary to provide implant coatings that release antibacterial substances. The scientific goal of this paper was to produce by electrophoretic deposition (EPD) a smart, chitosan/Eudragit E 100/silver nanoparticles (chit/EE100/AgNPs) composite coating on the surface of titanium grade 2 using different deposition parameters, such as the content of AgNPs, applied voltage, and time of deposition. The morphology, surface roughness, thickness, chemical and phase composition, wettability, mechanical properties, electrochemical properties, and silver release rate at different pH were investigated. Using lower values of deposition parameters, coatings with more homogeneous morphology were obtained. The prepared coatings were sensitive to the reduced pH environment.

The Chemical and Biological Properties of Nanohydroxyapatite Coatings with Antibacterial Nanometals, Obtained in the Electrophoretic Process on the Ti13Zr13Nb Alloy.

The risk of an early inflammation after implantation surgery of titanium implants has caused the development of different antimicrobial measures. The present research is aimed at characterizing the effects of nanosilver and nanocopper dispersed in the nanohydroxyapatite coatings, deposited on the Ti13Zr13Nb alloy, and on the chemical and biological properties of the coatings. The one-stage deposition process was performed by the electrophoretic method at different contents of nanomaterials in suspension. The surface topography of the coatings was examined with scanning electron microscopy. The wettability was expressed as the water contact angle. The corrosion behavior was characterized by the potentiodynamic technique. The release rate of copper and silver into the simulated body fluid was investigated by atomic absorption spectrometry. The antibacterial efficiency was evaluated as the survivability and adhesion of the bacteria and the growth of the biofilm. The cytotoxicity was assessed for osteoblasts. The results demonstrate that silver and copper increase the corrosion resistance and hydrophilicity. Both elements together effectively kill bacteria and inhibit biofilm growth but appear to be toxic for osteoblasts. The obtained results show that the nanohydroxyapatite coatings doped with nanosilver and nanocopper in a one-stage electrophoretic process can be valuable for antibacterial coatings.

Solvent-Free Synthesis of Phosphonic Graphene Derivative and Its Application in Mercury Ions Adsorption.

Functionalized graphene was efficiently prepared through ball-milling of graphite in the presence of dry ice. In this way, oxygen functional groups were introduced into material. The material was further chemically functionalized to produce graphene derivative with phosphonic groups. The obtained materials were characterized by spectroscopic and microscopic methods, along with thermogravimetric analysis. The newly developed material was used as an efficient mercury adsorbent, showing high adsorption efficiency. The adsorption isotherms were fitted using Freundlich and Langmuir models. The adsorption kinetics were fitted with pseudo-first order and pseudo-second order models. Adsorption selectivity was determined in the presence of cadmium ions and nickel ions. The presence of mentioned bivalent ions in the solution did not affect mercury adsorption efficiency.

Analytical and legislative challenges of sewage sludge processing and management.

ABSTRACT: This article presents the most popular methods of sewage sludge management and analytical techniques which could be a powerful tool in designing new sewage sludge management methods. Chemical analysis is also described as a vital point at the subsequent stages of technological processes control and sewage sludge quality assessment. It is also an instrument essential to maintaining control of processed sewage sludge introduced to the environment as ready-to-use materials. The sludge management method is conditioned by the compliance with legal acts concerning sludge management. The most important of these contain information regarding allowable concentrations of pollutants which can be released into the environment, and the most important declarations concerning sewage sludge management. Various analytical techniques and preparation methods that can be used during the monitoring of the managed and processed sewage sludge are described. The most important are chromatographic techniques, methods based on inductively coupled plasma, and mass spectrometry based methods.