In this work, bioaccumulation and biosorption characteristics of Cd2+ ions by both dead and living non-growing biomass of gram-positive bacteria Kocuria palustris and Micrococcus luteus isolated from spent nuclear fuel pools were compared. The radioindicator method with radionuclide 109Cd was used to obtain precise and reliable data characterizing Cd compartmentalization in bacterial cells. The following cellular distribution of Cd in living non-growing biomass after 4 h incubation in solutions containing different concentration of Cd2+ ions (100, 250, 500, 750 and 1000 µmol/L) spiked with 109CdCl2 under aeration at 30 °C were obtained: in M. luteus almost 85 % of Cd was localized on the cell surface and 15 % in cytoplasm. Similarly, in K. palustris 83 % of Cd was localized on the cell surface and 17 % in cytoplasm. The data were obtained by gamma spectrometry of extracts and solids after sequential extraction of biomass with 5 mM Ca(NO3)2 and 20 mM EDTA. Biosorption of Cd by non-living bacterial biomass is a rapid process strongly affected by solution pH and as was confirmed by FTIR analysis beside carboxylate ions also other functional groups such as amino and phosphate contribute to Cd binding by bacterial cell surfaces. Maximum sorption capacities Qmax (μmol/g) calculated from the Langmuir isotherm were 444 ± 15 μmol/g for M. luteus and 381 ± 1 μmol/g for K. palustris.
Agricultural wastes can be used as an alternative to the existing sorbents for the removal of metals or synthetic dyes from contaminated liquids. In this work, the fine powdered biomass of the hop (Humulus lupulus L.) variety Osvald's clone 72 and variety Bohemie as a sorbent for the removal of Cd from aqueous solutions of CdCl2 spiked with radionuclide 109Cd and synthetic dyes thioflavine T (ThT) or methylene blue (MB) from single dye solutions under conditions of batch systems was used. The maximum sorption capacity Q = 264 µmol Cd/g (d.w.) was found in the case of the leaf biomass of hop (H. lupulus L.) variety Osvald's clone 72 at the initial concentration of CdCl2 10,000 µmol/dm3, whereby the sorption capacity decreased in the order Qleaves : Qstems : Qroots = 1.0 : 0.8 : 0.7. The sorbed amount of Cd was removed from the hop biomass with the following increasing desorption efficiency of the extraction reagents: deionised H2O << 0.1 mol/dm3 HCl ≤ 0.1 mol/dm3 EDTA-Na2. Similarly as in the case of Cd sorption, the kinetics of ThT and MB sorption by the leaf biomass of the hop (H. lupulus L.) variety Bohemie were also showed as two-phase processes. The maximum sorption of ThT approx. Q = 19 mg/g (d.w.) and MB approx. Q = 70 mg/g (d.w.) were found within the range of the initial values of pH 4 – 7. The sorption of both dyes by the leaf biomass from single dye solutions decreased with increasing biomass concentration and on the other hand increased with increasing the initial concentrations of ThT or MB. The process of ThT and MB sorption was better described by the Langmuir model than the Freundlich model of sorption isotherm. From the obtained values of Qmax, it was found that in the case of MB the dried leaf biomass showed more than 2-times higher sorption capacity (Qmax = 184 mg/g; d.w.) in comparison with the value predicted for ThT. Obtained results suggest that dried plant biomass of hop (H. lupulus L.) as agricultural by-products can be used as a potential sorbent for both types of studied contaminants.
A hydroponic study involving lettuce plants (Lactuca sativa L.) as a leafy vegetable was conducted to evaluate the 137Cs uptake and translocation in plant tissues in dependence on the presence or absence of K+ or/and NH4+ ions in cultivation media according to Hoagland (HM) during 8 d plants growth under hydroponic conditions. Significant increase of the 137Cs+ uptake by lettuce plants and the decrease of 137Cs+ translocation efficiency from roots to leaves were observed in 50 % HM deficient in K+ and NH4+ ions. Speciation analysis using Visual MINTEQ program showed that at micromolar concentration of CsCl (5 μmol/dm3) in 50 % HM at pH 6.0 and 25 °C, cesium was occurred practically only in the free cationic Cs+ form − 98.8 %, with minor proportions of other cesium species: CsCl − 0.4 %, CsNO3 − 0.4 %, and CsSO4 - − 0.4 %. Surplus of Cl-, NO3- and SO42- ions in HM causes the increase of proportions of the cesium species CsCl, CsNO3 and CsSO4-, respectively at the expense of bioavailable Cs+ form. Radiocesium 137Cs taken up via roots was removed from lettuce leaves with high efficiency by boiling in diluted NaCl solution. At ambient temperature the extraction of 137Cs with diluted acetic acid was concentration and time dependent process, and was succeeded by leakage of tissue components absorbing at 260 nm. These findings are important for the risk assessment of radiocesium entry into the food chain via contaminated leafy vegetable.
This work deals with sorption of cationic synthetic dye thioflavine T (ThT) onto the river sediment obtained from the Váh River under conditions of batch and column system using spectrophotometric methods. We found that sorption of ThT onto river sediment was a rapid process with reaching of concentration equilibrium within 2 h of interaction. The values of distribution coefficient (DC) defined as concentration ratio [ThT]sediment : [ThT]solution were linearly increased with increasing concentration of river sediment in solution within the range Csediment 1.25 - 10.0 g/dm3 and minimally changed in the range of initial pH values 2 - 6. The increasing concentration of ThT in model solution caused exponentially decrease in the value of DC. The sorption processes characterized by dependence between equilibrium specific sorption Qeq and ThT concentration Ceq in solution were better described by adsorption isotherm according to Freundlich (R2 = 0.979) than according to Langmuir adsorption isotherm (R2 = 0.914). From evaluation of ThT sorption onto river sediment in column system containing of 5 cm sediment layer with 30 cm of water column on the basis of ThT concentration changes in infiltrated water we found that these processes were significantly dependent on the rate of infiltrated water flow through the sediment layer Riw as well as on qualitative and quantitative composition of water. The highest ThT desorption from the sediment layer was found in seepage of 50 % (v/v) ethanol (EtOH) solution through the sediment and efficiency of ThT desorption decreased in the order: 50 % (v/v) EtOH > 0.1 mol/dm3 HCl > deionized water. Obtained data from the point of view of physico-chemical characteristics of the river sediment, such as pH, pHzpc (potentiometric titration), cation-exchange capacity (CEC) and elemental composition (X-ray fluorescence spectrometry), was also discussed
The aim of the present work is to characterize the soil additive derived from sewage sludge as potentially economically acceptable material for agricultural production as well as for soil and environment protection. The soil additive consisting of sewage sludge obtained from the wastewater treatment plant Pannon-Víz Zrt. (Győr, Hungary) and agricultural byproducts represented by wastes from grain mill industry and crushed corn cobs was prepared using the low-capacity granulator equipment constructed by Energy Agency Public Nonprofit Ltd. (Hungary). The characterization of sewage sludge as primary composite and prepared soil additive includes the determination of physico-chemical parameters such as pH determined in suspension with distilled water, 0.01 mol/dm3 CaCl2 or 1 mol/dm3 KCl solutions, pHzpc predicted by potentiometric titration and ProtoFit software, water holding capacity (WHC), cationexchange capacity (CEC) and total organic carbon (TOC). The elemental analysis by X-ray fluorescence spectrometry revealed that sewage sludge as well as prepared soil additive contain significant amount of Zn and Cu as important microelements in plant nutrition. Also, it was found that prepared soil additive represents the considerable source of a significant proportion, strong bound and in this way gradually released microelements. Obtained results suggest on the application potential of prepared soil additive in agricultural production as well as in remediation and reclamation of contaminated or degraded soil.
Concentration of available zinc from soils is the primary concern in assessment of its toxicity or essentiality for plants. This study evaluates the changes in chemical extractable Zn from three Slovak typical soils with simultaneous extractions as tools of zinc bioavailability. We found out that extractability of binding zinc decreased in order Na2EDTA, Mehlich 3, Mehlich 2, NH4NO3 and CaCl2 for all soil samples. Using flow-through stripping chronopotentiometry (SCP) and atomic absorption spectrometry (GFAAS) we found out that maximum of soil zinc was removed by organic ligands. Lability of Zn determined by isotopic dilution method using 65Zn and γ-spectrometry showed the significant decrease of isotopic exchangeable zinc fraction (E-value) with decrease of soil reaction. Obtained E-values of uppermost soil horizons showed the zinc lability ranged from 20 to 39%. Our research confirmed the effect of soil reaction, composition and physico-chemical characteristics to Zn lability. For further assessment of zinc bioavailability is needed to find the correlation and effects of structural changes and aging in studied soils
Production of unsettleable sewage sludge with high water content is one of the problems of intensification of industrial activities and environmental protection. Sewage sludge with low toxic metals concentrations can be utilized as fertilizer and soil conditioner in agriculture. For determination of metal bioavailability, a wide range of extraction protocols and fractionation analyses can be used. We studied the distribution and quantified the leaching and bioavailability of zinc from dried anaerobic sludge by simultaneous, multi-step and three different sequential extraction protocols. For determination of zinc, the galvanostatic stripping chronopotentiometry (SCP) and electrothermal atomic absorption spectrometry (ETAAS) were used. The distribution of Zn in sequential extraction protocols was determined using a fivestep chemical fractionation procedures (BCR, Tessier and Van Hullebusch protocols). The potential bioavailability (0.9% NaCl, 0.1 mol/dm3 HCl, 0.1 mol/dm3 HNO3, 0.1 mol/dm3 CH3COOH, 0.1 mol/dm3 Na2EDTA, 0.1 mol/dm3 CaCl2, 0.1 mol/dm3 MgCl2, 0.1 mol/dm3 (NH4)2C2O4.H2O extraction) and pseudo total (aqua regia extraction and ETAAS analyses) content of Zn in sludge was determined. The amount of aqua regia extractable zinc in sludge samples was 650 ± 12 mg/kg (d.w.). We found out that the zinc was extractable from anaerobic sludge in first hour of contact time for all tested agents. Zinc was extracted with highest efficiency by 0.1 mol/dm3 (NH4)2C2O4.H2O, 0.1 mol/dm3 HCl and 0.1 mol/dm3 Na2EDTA. Sequential extraction protocols showed that the maximum extractable amount of zinc 126.3 ± 2.6 mg Zn / kg d.w. was bound to organic matter and sulfides. High concentrations of zinc in residual fractions were leachable under extraction conditions of strong acids only.
This study investigated the concentrations of polycyclic aromatic hydrocarbons (PAHs) in pyrogenic carbonaceous materials (PCM) produced from three waste materials during slow pyrolysis at 400 and 500°C. As feedstocks bone meal (BM), biogas slurry (BC) and chicken manure (CM) were used. As potentially problematic substances 1- and 2- methylnaphthalene were analysed as indicators for methylated hydrocarbons in pyrolysis products. The phytotoxic effect of soil amendments was evaluated by a standard cress germination test with Lepidium sativum L. The analysis showed higher concentrations of the sum of 16 US-EPA PAHs in samples produced at lower temperature and in samples produced from biogas slurry. Concentrations of 1- and 2-methylnaphthalene showed similar trends with concentrations in a range of 35-205% of the sum of 16 PAHs. Germination tests showed inhibition effects of products from biogas slurry when applied in concentrations of ≥ 10 % to standard substrate. Apparently pyrolysis of biogas slurry requires special attention to avoid accumulation of PAHs and methylated naphthalenes.
Heavy metals are taken up by the vascular plant root system from water solutions in cationic forms. Subsequently, during both short and long distance transport to other plant tissues, cation forms are incorporated to many bioorganic compounds differing in stability, ionic character and physico-chemical properties such as solubility in lipid structures and mobility across cell membrane systems. Many sequential and single step extraction methods have been elaborated for characterization of the role of individual components of plant cells components in transport and detoxication of heavy metals. In our study, dry biomass of giant reed (Arundo donax L.) grown in hydroponic media spiked with 65ZnCl2 and 109CdCl2 was treated with dithizone solutions as complexing ligand in order to convert free Zn2+ and Cd2+ ions to corresponding dithizonates. Treatment with dithizone showed that up to 67 % of the total plant Cd and 56 % of the total plant Zn were transformed to dithizonate complexes extracted with chloroform. Extraction of biomass with Folch reagent showed that up to 48 % of the total root cadmium and up to 18 % of the total shoot cadmium is bound in lipid fraction. Zinc was not found in lipid fraction of root and shoot. Derivatization of the dried root and shoot lipid fraction by dithizone showed that two third of Cd in root and practically all Cd in shoot lipid fraction could be transformed to Cd-dithizonate. Methods of biomass treating with complexing ligands and a method of sequential extraction procedures with non-polar organic solvents and radiotracer methodology seem to be useful methods for the study of metal speciation and distribution in vascular plants
This paper evaluates the effect of simulated conditions of artificial aging on sorption capacity of two types of biochar. These were produced by slow pyrolysis from different feedstock - beech wood chips (BC A) and garden green waste residues (BC B). Cadmium served as a model for potentially toxic metals. Twenty freeze-thaw cycles were used to simulate physical aging. The determination of biochar physicochemical properties showed main changes in CEC and SA values of aged sorbents. The maximum sorption capacities of aged BC A sorbent were higher by about 26 % and aged BC B sorbent by about 20% compared to Qmax of non-aged biochar. Qmax of aged BC B peaked at 9.4 mg g-1 whereas BC A sorbed significantly less Cd. FT-IR analyses confirmed the changes in structural composition and content of functional groups on biochar surfaces. The artificial physical aging model was assessed as an efficient tool for investigation of natural weathering conditions.