Experimental Treatment of Hazardous Ash Waste by Microbial Consortium Aspergillus niger and Chlorella sp.: Decrease of the Ni Content and Identification of Adsorption Sites by Fourier-Transform Infrared Spectroscopy.

Despite the negative impact on the environment, incineration is one of the most commonly used methods for dealing with waste. Besides emissions, the production of ash, which usually shows several negative properties, such as a higher content of hazardous elements or strongly alkaline pH, is problematic from an environmental viewpoint as well. The subject of our paper was the assessment of biosorption of Ni from ash material by a microbial consortium of Chlorella sp. and Aspergillus niger. The solid substrate represented a fraction of particles of size <0.63 mm with a Ni content of 417 mg kg-1. We used a biomass consisting of two different organisms as the sorbent: a non-living algae culture of Chlorella sp. (an autotrophic organism) and the microscopic filamentous fungus A. niger (a heterotrophic organism) in the form of pellets. The experiments were conducted under static conditions as well as with the use of shaker (170 rpm) with different modifications: solid substrate, Chlorella sp. and pellets of A. niger; solid substrate and pellets of A. niger. The humidity-temperature conditions were also changed. Sorption took place under dry and also wet conditions (with distilled water in a volume of 30-50 ml), partially under laboratory conditions at a temperature of 25°C as well as in the exterior. The determination of the Ni content was done using inductively coupled plasma optical emission spectrometry (ICP-OES). The removal of Ni ranged from 13.61% efficiency (Chlorella sp., A. niger with the addition of 30 ml of distilled water, outdoors under static conditions after 48 h of the experiment) to 46.28% (Chlorella sp., A. niger with the addition of 30 ml of distilled water, on a shaker under laboratory conditions after 48 h of the experiment). For the purpose of analyzing the representation of functional groups in the microbial biomass and studying their interaction with the ash material, we used Fourier-transform infrared (FTIR) spectroscopy. We observed that the amount of Ni adsorbed positively correlates with absorbance in the spectral bands where we detect the vibrations of several organic functional groups. These groups include hydroxyl, aliphatic, carbonyl, carboxyl and amide structural units. The observed correlations indicate that, aside from polar and negatively charged groups, aliphatic or aromatic structures may also be involved in sorption processes due to electrostatic attraction. The correlation between absorbance and the Ni content reached a maximum in amide II band (r = 0.9; P < 0.001), where vibrations of the C=O, C-N, and N-H groups are detected. The presented results suggest that the simultaneous use of both microorganisms in biosorption represents an effective method for reducing Ni content in a solid substrate, which may be useful as a partial process for waste disposal.

Microbial Features Indicating the Recovery of Soil Ecosystem Strongly Affected by Mining and Ore Processing.

Tailings-derived soils formed from waste materials produced during mineral processing often exhibit extremes of pH, low content of organic matter and limited nutrient availability. The success of site revitalization depends mostly on the ability to maintain natural soil functions. We analyzed technogenic sediments from four selected localities in Slovakia defined as environmental burdens: Slovinky (SLS, SLD), Markusovce (MAS, MAD), Lintich (LIS, LID), Horná Ves (HVS, HVD) in the presented research. None of these sites has long been used for its original purpose. In all localities, the concentrations of several risk elements (As, Ba, Cd, Co, Cr, Cu, Ni, Pb, Zn) still significantly exceed the statutory limit values. Besides the content of risk elements, the amounts of organic carbon, total nitrogen, pH value and moisture level in technogenic substrates were determined. We evaluated selected microbiological parameters, including microbial biomass carbon (MBC), microbial respiration and cellulolytic activity to determine how soil organisms tolerate long-term pollution. In general, the values of microbiological parameters were not as low as one would expect. The results confirmed a negative correlation between MBC content and concentrations of several toxic metals (Co, Cr, Cu, Ni, Zn). The values of assessed microbial indicators were in several cases comparable to those in natural soils. We noticed the lowest metabolic quotient values (qCO2) in the heavily polluted locality HVS. The microbial quotient (qMic) was low in every locality except HVS, where the substrate availability index (SAI) was highest. The soil microbial community properties have shown that, despite adverse conditions, these emerging soils allow the growth and development of microorganisms to such an extent that they can adequately use available (although limited) nutrients. The data obtained suggest that these severely impacted soil ecosystems can restore their original environmental functions in time.

Composite films prepared from agricultural by-products.

In our study we used holocelluloses from sugar beet and bagasse for film preparation. Films from sugar beet holocellulose have better mechanical properties than from bagasse holocellulose. By subsequent carboxymethylation of bagasse holocellulose, films with better properties were produced. Specimens prepared from combined sugar beet and bagasse carboxymethylated holocellulose had the best mechanical properties. The results could be explained by the ratios of cellulose, arabinan, polygalacturonan and xylan content in individual films, based on the elemental analysis data. The use of microwaves to prepare holocellulose film speed up the process, but negatively affected the mechanical properties. Lignin content of the sugar beet holocellulose and bagasse samples was low and did not affect the mechanical properties. Both types of agricultural by-products could be used for preparation of composite film with high strength and stiffness suitable for broad range of applications.

Biological properties of extremely acidic cyanide-laced mining waste.

With respect to acidic, cyanide-laced tailings, the data about in situ toxicity and biological activity in highly polluted environment are often lacking. The aim of this study was to assess the microbial characteristics, composition of oribatid mite species, and level of genotoxic impact on plants in the area of inactive tailings pond (Horná Ves, Kremnica region). Sampling of the tailings, soils and selected plant species was carried out in spring of 2012. Trace element analysis (inductively coupled plasma emission and mass spectrometry) showed that concentration of Pb, Zn, and Cu in the tailings is approximately in thousands of ppm (mg kg(-1)). Amount of lead exceeded 16,000 mg kg(-1), which is perceived as the biggest threat with respect to possible toxicity. The risk is accentuated by extremely acidic pH of the tailings material which approached 2. In such conditions great mobility of (divalent) heavy metal cations is expected. The total cyanide concentration in the tailings was 472 mg kg(-1). Results of performed tests and measurements suggest that microbial activity at the tailings site (and its close environment) is hampered markedly. In the sludge material we detected low abundance of soil bacteria (2.08 × 10(4) CFU) and predominance of slowly growing K-strategists. On the other hand, the content of microbial C in the sludge sample was not too low, considering its extreme acidity and high amount of risk elements. In the same sample, just one mite species, Oppiella (O.) uliginosa (Willmann 1919), was identified. Also in case of the dam site the abundance of mites was considerably lower in comparison to reference sample. Values of Oribatida abundance were in positive correlation with values of microbial biomass carbon. Results of the pollen grain abortivity test, applied in situ on chosen plant species, indicated substantial presence of genotoxicity in the environment. Total induction index of tailings pond reached 3.59(±2.4) which expresses also total load of locality, comparing to natural biotope. In case of the technogenic sediment, the value was more than three times higher.

Biological activity of the metal-rich post-flotation tailings at an abandoned mine tailings pond (four decades after experimental afforestation).

In the spring 2012, post-flotation tailings of the inactive impoundment Lintich (Slovakia) were sampled. In the impoundment sediment and also in its surrounding, we detected concentration of Pb, Zn, Cd, Cu, and Ba exceeding limiting values. We detected low values of the microbial biomass carbon and microbial activity in the impoundment sediment (LiS) and its dam (DAM) along with potential respiration stayed relatively low and therefore also substrate availability index and metabolic quotient (qCO2) were higher in the control sample (REF) than in the LiS and the DAM. The low qCO2 level indicates that microbial community, despite of dangerously high levels of heavy metals in sediment, is still able to sufficiently utilize sources of available organic carbon. Anyway, we could doubt function of the metabolic index as universal indicator of environment conditions, regarding the anthropogenic substrates. We confirmed changes in composition of the mite communities along gradient dam-impoundment. The percentage of eudominant, recendent, and subrecendent species increased at the expense of dominants and subdominants, all together with decreasing diversity and equitability of the community. We identified species Chamobates borealis, Carabodes rugosior, Metabelba propexa, and Pergalumna nervosa with negative respond under the heavy metal stress. Species Adoristes ovatus was indifferent and Dissorhina sp., Hafenrefferia gilvipes, and Oppiella nova prospered under the loaded conditions. Forty years after experimental afforestation, we expect specific community of actively surviving microorganisms and Oribatida species detected in the DAM are usual in the greatly degraded habitats or on sites in the early succession.

Cationization of heparin for film applications.

Trimethylammonium-2-hydroxypropyl-(TMAHP) spacer was introduced into heparin (H) and the prepared films were characterized by elemental analysis, NMR, SEC-MALS, TG/DTG/DTA, AFM and mechanical tester. When quaternized at the ratio of H/NaOH/alkylating agent/H2O=0.1-1/0-2/0.1-1/50-500 mmol, H was substituted at A6 and A3 positions. The formation of double-substituted structures by substitution of free hydroxyl group of the previously introduced TMAHP substituent is evident. In the absence of NaOH (H/GTMAC/H2O=1:1:500) the most drastic decrease of M(n) to 8.639 kg/mol and M(w)/M(n) at 1.48 was observed in comparison to H (Mn=9532 g/mol with M(w)/M(n)=1.38). The film mechanical properties were better on H (E=4030 MPa; σ(b)=65 MPa; ɛ(b)=4.6%) than on quaternized specimens (E=2500-3340 MPa; σ(b)=25-40 MPa; ɛ(b)=1.7-1.8%). The AFM images did not prove relation between mechanical properties and surface shape.

Carboxymethylated-, hydroxypropylsulfonated- and quaternized xylan derivative films.

Under alkaline/water conditions carboxymethyl, 2-hydroxypropylsulfonate and trimethylammonium-2-hydroxypropyl groups were introduced into xylan in one step with the goal to prepare film specimens. The materials were characterized by NMR, SEC-MALS, TG/DTG/DTA, AFM and mechanical testing. The properties of triple, double and mono-substituted materials were compared. The numerical molar masses of the specimens were from 12.3 to 17.6 kg/mol with Mw/Mn from 1.27 to 1.34. The elastic modulus values are decreasing in order: xylan (X; 7354 MPa)>carboxymethyl xylan (CX; 6090MPa)>2-hydroxypropylsulfonate xylan (SX; 6000 MPa)>carboxymethyl/2-hydroxypropylsulfonate xylan (CSX; 4490 MPa)>quaternized xylan (QX; 3600 MPa)>carboxymethyl/quaternary/2-hydroxypropylsulfonate xylan (CQSX; 3380 MPa)>carboxymethyl/quaternary xylan (CQX; 2805 MPa). The onset temperatures of SX (214°C), CQSX (212°C), QSX (211°C) and CQX (207°C) were higher than for X (205°C). The roughness values of the film surfaces (3.634-18.667 nm) are higher on top than on the bottom of the specimen.

Quaternized and sulfated xylan derivative films.

Xylan quaternized sulfate films were prepared from beech xylan (X) and compared with fully sulfated xylan films (XS). When quaternized xylan (QX) was prepared in the first step (DS(Q)=0.55), than by sulfation of QX in the second step the fully substituted ampholytic derivative (QXS; DS(Q)=0.33; DS(S)=1.67) could be obtained. By sulfation in first step, xylan sulphate (SX, DS(S)=0.70) was obtained and by subsequent quaternization, SXQ film with DSQ=0.55 and DSS=0.33 which contained partially unsubstituted hydroxyls. The molar masses (M(n)) of the film's soluble parts were increasing in order X

Unexplored possibilities of all-polysaccharide composites.

Composites made solely from polysaccharides are mostly ecological because they can degrade without leaving behind ecologically harmful residues, in contrast to composites which contain synthetic polymers. Herein, the following groups of all-polysaccharide composites (APCs) are discussed: an all-cellulose group that includes cotton composites, cellulose combined with other polysaccharides, as well as those based on chitin/chitosan, heparin, hyaluronan, xylan, glucomannan, pectin, xyloglucan, arabinan, starch, carrageenan, alginate, galactan as one of the components in combination with other polysaccharides. They can be used in medical, paper, food, packing, textile, electronic, mechanical engineering and other applications. The composites were tested for absorptivity, biodegradability, crystallinity, rheology, and mechanical, optical, separation, gelling, pasting, film-forming, adhesive, antimicrobial properties, as well as water vapor permeability, water repellency, dye uptake, and fire-retardancy. Except for food applications, composites based on more than two types of polysaccharides have rarely been used and many possible combinations remain unexplored.

TG/DTG/DTA evaluation of flame retarded cotton fabrics and comparison to cone calorimeter data.

Unbleached cotton fabrics (UCF) with 12.5% polypropylene scrim treated with two phosphate-urea based fire-retardant (FR) formulations were evaluated for FR properties using thermogravimetry/differential thermogravimetry/differential thermal analysis (TG/DTG/DTA) method. In addition to testing the two FR-treated unbleached cotton fabrics (CF-FR1 and CF-FR2), bleached cotton fabric (BCF) treated with the two FR formulations (BCF-FR1 and BCF-FR2) was evaluated. Both formulations were washable with add-on of FR chemicals at 18.7% (FR1) or 17.4% (FR2) for UCF and 22.5% (FR1) or 24.9% (FR2) for BCF. The decreasing order of sums at maximal rates of samples degradation in air environment according to DTG method was: BCF (21.40%/min)>UCF (12.91%/min)>BCF-FR2 (12.83%/min)>BCF-FR1 (11.68%/min)>CF-FR2 (10.20%/min)>CF-FR1 (9.73%/min). It indicates that both formulations cause the decrease of thermooxidation of the products at slower rates than the starting material. Several endo- and exothermic peaks observed by DTA in inert and oxidative environment gives additional information about the degradation process. The order of decreasing thermal responses of the studied samples based on sums of DTA peak values of endothermic and exothermic peaks in air environment is: UCF (0.597 °C/mg)>BCF (0.120 °C/mg)>CF-FR1 (0.089 °C/mg)>BCF-FR1 (0.077 °C/mg)>CF-FR2 (0.062 °C/mg)>BCF-FR2 (0.053 °C/mg). This is in agreement with the cone calorimeter results according to which the flammability properties are improving with the decreasing heat release rates or ignition time prolongation in order: UCF>CF-FR1>CF-FR2. The advantage of TG/DTG/DTA method is slower linear heating rate, which allows the more detailed evaluation of the light and flammable cotton fabric.