Alginate beads containing water treatment residuals for arsenic removal from water—formation and adsorption studies

Water treatment residuals (WTRs) produced in large quantities during deironing and demanganization of infiltration water, due to high content of iron and manganese oxides, exhibit excellent sorptive properties toward arsenate and arsenite. Nonetheless, since they consist of microparticles, their practical use as an adsorbent is limited by difficulties with separation from treated solutions. The aim of this study was entrapment of chemically pretreated WTR into calcium alginate polymer and examination of sorptive properties of the obtained composite sorbent toward As(III) and As(V). Different products were formed varying in WTR content as well as in density of alginate matrix. In order to determine the key parameters of the adsorption process, both equilibrium and kinetic studies were conducted. The best properties were exhibited by a sorbent containing 5 % residuals, formed in alginate solution with a concentration of 1 %. In slightly acidic conditions (pH 4.5), its maximum sorption capacity was 3.4 and 2.9 mg g^?1 for As(III) and As(V), respectively. At neutral pH, the adsorption effectiveness decreased to 3.3 mg As g^?1 for arsenites and to 0.7 mg As g^?1 for arsenates. The presence of carboxylic groups in polymer chains impeded in neutral conditions the diffusion of anions into sorbent beads; therefore, the main rate-limiting step of the adsorption, mainly in the case of arsenates, was intraparticle diffusion. The optimal condition for simultaneous removal of arsenates and arsenites from water by means of the obtained composite sorbent is slightly acidic pH, ensuring similar adsorption effectiveness for both arsenic species.     

Conditions for the development of anaerobic digestion technologies using the organic fraction of municipal solid waste: perspectives for Poland

This article outlines problems related to the location of facilities designed to treat the organic fraction of municipal solid waste (OFMSW). Anaerobic digestion (AD) facilities are investigated as a treatment option, while taking into account the aspects of renewable energy generation. This research has been spurred on by the relationship between waste management, energy generation issues and spatial planning procedures. The analysis is focused on urban and semi-urban areas of medium and large cities. One of the most difficult issues associated with siting of waste processing plants is its integration with local infrastructures, avoiding conflicts and negative environmental impacts at the same time. This research aims to analyse possible locations for AD plants fuelled by OFMSW in Poland. Based on the experience gained from other countries and lessons learnt from the analysis of existing facilities in Europe, conditions for the location of this type of waste treatment plants have been defined, with the focus on economic, environmental and social issues. Most likely, the results of the multicriteria decision analysis for siting of municipal solid waste AD plants (M-BIST tool) could be transferred to other countries, especially those with a comparable GDP level and a similar framework for a waste management system.     

Estimation of wind blown dust emissions in Europe and its vicinity

The assessment of the wind blown dust emission for Europe and selected regions of North Africa and Southwest Asia was carried out using a mesoscale model. The mesoscale model was parameterized based on the current literature review. The model provides data on PM₁₀ emission from several dust reservoirs (anthropogenic, agriculture, semi- and natural) with spatial resolution of 10 × 10 km and temporal resolution of 1 h. The spatial variability of PM₁₀ emission depends on soil texture, land cover/land use as well as meteorological conditions. Lands covered with water or permanently wet were excluded from the model. The land covered with vegetation is treated as dust reservoir whose dust emission capacity depends on the type of vegetation and cover. The dust reservoirs are divided into reservoirs with stable and unstable surface. The changes of emission in time depend on meteorological parameters.The wind blown dust emission should be treated as a non-continuous spatio-temporal process. The emissions are estimated with high uncertainty. The estimated PM₁₀ yearly total load emitted by wind from the European territory is highly differentiated in space and time and is equal to 0.74 Tg. The total load of PM₁₀ emitted by wind from North African and Southwest Asian land surface located in the vicinity of European boundaries is assessed as nearly 50% (0.43 Tg) of the total load estimated for the whole Europe.The average yearly PM₁₀ emission factor for Europe was estimated at 0.139 Mg km^?2.The PM₁₀ emission from agricultural areas is estimated at 52% of the total wind blown emission from the domain of the European Union project “Improving and applying methods for the calculation of natural and biogenic emissions and assessment of impacts to the air quality” - NatAir.PM₁₀ emission factor for natural areas of Europe is estimated at 0.021 Mg km^?2. Appropriate factors for agricultural areas and anthropogenic areas are 0.157 Mg km^?2 and 0.118 Mg km^?2, respectively. The latter two factors are probably underestimated due to omitting in the model of other dust emission mechanisms than aeolian erosion.     

Seasonal and spatial variability of Po,U and Pu levels in the river catchment area assessed by application of neural-network based classification

The present study deals with the application of self-organizing maps (SOM) in order to model, classify and interpret seasonal and spatial variability of ²¹⁰Po, ²³⁸U and ^239+240Pu levels in the Vistula river basin. The data set represents concentration values for 3 alpha emitters (²¹⁰Po, ²³⁸U and ^239+240Pu) measured in surface water samples collected at 19 different sampling locations (8 in major Vistula stream while 11 in right or left Vistula tributaries) during four seasons (winter, spring, summer and autumn) in the framework of a one-year quality monitoring study. The advantages of an SOM algorithm, its classification and visualization ability for environmental data sets, are stressed. The neural-network based classification made it possible to reveal specific patterns related to both seasonal and spatial variability. In the middle and upper part of Vistula catchment as well as in the right-shore tributaries, concentrations of ²¹⁰Po and ²³⁸U during summer and winter are the lowest. Concentrations of ²¹⁰Po and ²³⁸U increase significantly during spring and autumn in the Vistula river catchment, especially in the delta of Vistula river. High concentration of anthropogenic originated ^239+240Pu indicates “site-specific” character of pollution in two large left-shore tributaries located in the middle part of the Vistula drainage area. Efficient classification of sampling locations could lead to an optimization of river radiochemical sampling networks and to a better tracing of natural and anthropogenic changes along Vistula river stream.     

An appraisal of changes in seasonal water quality during passage through a shallow reservoir in Western Poland

Following restoration changes in Antoninek Reservoir physico-chemical and biological processes in the water column and bottom sediments were measured to outline mechanisms of changes in nitrogen, phosphorus and organic matter concentrations during water flow through this reservoir. Intensive mineralisation of organic matter in the shallow sediments stimulated primary production and influenced increasing ammonia and nitrite nitrogen concentrations. Two main factors affected concentrations of phosphorus: (1) its presence in the external loads of river waters entering the reservoir, more important in the colder seasons as the water discharge was higher and (2) from the internal loads coming from bottom sediments. The quality of the river water during its flow through this reservoir improved for most parameters and seasons. However, concentrations of nutrients were still high in waters flowing out from the reservoir and in some months they were higher in the outflow than in waters entering the reservoir.     

Optimisation of pressurised liquid extraction for elimination of sulphur interferences during determination of organotin compounds in sulphur-rich sediments by gas chromatography with flame photometric detection

A simple method for species-selective analysis of organotin compounds (OTCs) (butyl and phenyl) in sediments was developed. The sample preparation procedure was specifically optimised for sulphur-rich sediments to eliminate interferences from elemental sulphur and organosulphur compounds. Tin species were extracted from sediment samples using pressurised liquid extraction technique (PLE), ethylated - with simultaneous extraction to isooctane - in aqueous phase with sodium tetraethylborate (NaBEt(4)) and separated/detected by gas chromatography with flame photometric detection (GC-FPD). PLE operational variables (extraction temperature and pressure, solvent composition and number of static extraction steps) and extract handling routine were fine-tuned to minimise the amount of extracted interferents while keeping OTCs recovery at an acceptable level. Best results were obtained after extraction of sediment samples with methanol/water (75% v/v methanol) solution of acetic acid/sodium acetate with tropolone addition (0.6 g l(-1)). Derivatisation of low temperature, high-pressure (50 degrees C, 13.8 MPa) extracts gives isooctane extracts which are clean enough to be directly analysed by GC-FPD without any further cleanup. Interferences from elemental sulphur were completely eliminated while concentrations of other interferents were reduced to the level not impairing quantitation of OTCs under the study. No negative effects in terms of chromatographic column deterioration were observed after repeated injections of such extracts. Two certified reference materials, BCR646 and PACS-2, were analysed to assess performance of the method. Recoveries of all OTCs under the study, except MBT, were in the range of 91-114%. MBT extraction efficiency was low (34-47%) therefore the method is unsuitable for precise determinations of this compound.     

Electrochemical and FTIR studies of the mutual influence of lead(II) or iron(III) and phenol on their adsorption from aqueous acid solution by modified activated carbons

Cyclic voltammetry and spectral FTIR studies of the influence of activated carbon surface modification on the co-adsorption of metal cation (lead or iron) and phenol from aqueous acidic solution were carried out. The diversity in surface chemical structure was achieved by applying different procedures of inorganic matter removal and by modifying the carbon samples in various ways: heating under vacuum, aminoxidation in an ammonia-oxygen atmosphere, oxidation with concentrated nitric acid. The quantities of adsorbed metal ions (Pb(2+) or Fe(3+)) and phenol from solutions containing cation or phenol separately or in a mixture were determined. The adsorption capacity from acidic aqueous acidic solution depends on the chemical properties of the activated carbon surface (e.g., decrease in phenol adsorption with relative lower basicity of the adsorbent). The electrochemical parameters of electrodes made from the carbon samples were estimated, and some possible electrochemical reactions were determined from voltammograms recorded in acid electrolyte solution containing adsorbed species (separately or as a mixture). Relationships were found between metal ion adsorption and electrochemical behavior of Pb(2+)/Pb(4+) and Fe(3+)/Fe(2+) couples on the one hand, and the presence of phenol in the solutions tested and the influence of surface chemistry of the carbon electrodes on electrochemical processes on the other. The changes in adsorption capacity with respect to the adsorbates used and the changes in FTIR spectra of the carbons as a result of adsorption and/or coupling phenol molecules are discussed.     

Effect of coumaphos on cholinesterase activity, hematology, and biochemical blood parameters of bovines in tropical regions of Mexico

To assess the effect of coumaphos [O-(3-chloro-4-methyl-2-oxo-2H-1-benzopyran-7-yl) O,O-diethyl phosphorothioate] exposure on physiological responses during bovine production, acetylcolinesterase (AChE) and butyrylcholinesterase (BuChE) activities were measured in whole blood, erythrocytes, and plasma of healthy male steers (Bos Taurus x Bos indicus) sprayed with coumaphos at a non-lethal dose of 1 mg kg(- 1) body weight per day once every 14 (in vivo group) or 21 days (southern and central groups). Coumaphos topically administered at 1 mg/kg body weight per day to cattle under normal management practices in tropical areas produced a significant inhibition in erythrocyte (RBC) AChE and BuAChE activities when compared to baseline levels. RBC-AChE activity for the in vivo group decreased 71.3% (P < 0.05) and BuChE activity 59.1% (P < 0.05); RBC-AChE activity decreased 55.1% (P < 0.05) (southern group) and 43.4% (P < 0.05) (central group). Compared to the control specimens, steers from in vivo, southern, and central groups after 150 days of exposure had lower (P < 0.05) leukocyte count, absolute lymphocyte, erythrocyte, and platelet counts. Decreases in RBC-AChE activities correlated with decreased lymphocyte (r = 1.000, p = 0.01), erythrocyte (r = 1.000, p = 0.003), and platelet counts (r = 0.841, p = 0.036). Significantly increased BUN levels (P < 0.05) correlated with the decrease in RBC-AChE activities (r = - 0.997, p = 0.047) and with the decrease in absolute red blood cell (r = - 0.883, p = 0.020) and lymphocyte (r = - 0.825, p = 0.043) counts; increased (P < 0.05) total plasma protein levels correlated with the decrease in RBC-AChE activities (r = -0.998, p = 0.043), absolute red blood cell (r = - 0.998, p = 0.040), lymphocyte (r = - 0.893, p = 0.017), and platelet (r = -0.855, p = 0.030) counts. The physiological responses correlated with the erythrocyte acetylcholinesterase inhibition could be considered as early indicators or warning responses of bovine exposures to organophosphorus pesticides (OPs).     

NMR study of the humification process during sewage sludge treatment

Humic acids, extracted from sludge at the biologic-mechanical sewage treatment plant in Jastrzebie Zdroj, have been investigated by means of (1)H, (13)C and (31)P NMR spectroscopy. Sludge samples for studies were taken from the primary settling tank, the nitrification chamber, the digestion chamber and the sludge drying beds. The (1)H NMR analysis of humic acid extracted from sludge at various stages of sewage treatment confirmed the presence of the functional groups that are characteristic for humic substances, and the analysis showed changes in their relative intensities. The (13)C NMR indicated that the aromatisation of the humic acid increased during sewage treatment. Moreover, the analysis of the (31)P NMR spectra allowed us to observe the changes in the phosphorus groups of the studied humic acids.     

Co-combustion of dried sewage sludge and coal in a pulverized coal boiler

More than 1.1 million tons of municipal and industrial sewage sludge is produced annually in Poland. Most of this sewage sludge is landfilled or used for recultivation and fertilization of soil. After accession of Poland to the EU, large investments are planned for wastewater treatment, so it is expected that the amount of sewage sludge produced in Poland will grow in the near future. It is well known that the combustion of sewage sludge is becoming a more and more popular utilization method of such waste. Unfortunately, the current situation in Poland makes it impossible to incinerate the sewage sludge because of a lack of incinerators. One possible solution for Poland is the co-firing of dried sewage sludge in existing coal-fired utility boilers. This article presents results of initial Polish industrial trials of dried municipal sewage sludge and hard coal co-combustion in an OP-230 pulverized coal boiler. Such a solution was shown to be technically viable and not to require changes to the existing technological system. Cocombustion of sewage sludge with coal in power plants seems to be the best solution for sludge utilization in the near future in Poland.