Valorisation of Lignocellulosic Wastes, the Case Study of Eucalypt Stumps Lignin as Bioadsorbent for the Removal of Cr(VI).

The main objective of this work was to assess Eucalyptus globulus lignin as an adsorbent and compare the results with kraft lignin, which has previously been demonstrated to be an effective adsorbent. Eucalypt lignin was extracted (by the dioxane technique), characterised, and its adsorption properties for Cr(VI) ions were evaluated. The monomeric composition of both types of lignin indicated a high content of guaiacyl (G) and syringyl (S) units but low content of p-hydroxyphenyl (H), with an H:G:S ratio of 1:50:146 (eucalypt lignin) and 1:16:26 (kraft lignin), as determined by Py-GC/MS. According to elemental analysis, sulphur (2%) and sodium (1%) were found in kraft lignin, but not in eucalypt lignin. The adsorption capacity of the eucalypt lignin was notably higher than the kraft lignin during the first 8 h, but practically all the ions had been absorbed by both the eucalypt and kraft lignin after 24 h (93.4% and 95%, respectively). Cr(VI) adsorption onto both lignins fitted well using the Langmuir adsorption isotherm model, with capacities of 256.4 and 303.0 mg/g, respectively, for eucalypt and kraft. The study's overall results demonstrate the great potential of eucalypt lignin as a biosorbent for Cr(VI) removal from aqueous solutions.

'Green' coagulant application with activated carbon: dosing sequence and removal of selected micropollutants and effluent organic matter from municipal wastewater.

Combination of 'green' coagulation and powdered activated carbon adsorption was tested for removal of benzophenone (BP), benzophenone-3 (BP-3) and caffeine (CF) from treated municipal wastewater at realistic concentration levels (1-2 µg/L). At the same time it was tracked how the process affected effluent organic matter (EfOM) by measuring chemical oxygen demand (COD). Green coagulant was produced from dry common bean seed in laboratory. Combined coagulation-adsorption experiments were performed by applying different dosing sequences of process materials. Removal of hydrophobic BP and BP-3 by separate adsorption (from 79 to 98%) was not significantly hindered by the addition of the coagulant (activated carbon dose of 5 or 20 mg/L). However, in some cases negative effects were observed for hydrophilic caffeine, depending on the carbon dose, dosing sequence and presence of total suspended solids (TSS). Thus, when coagulant was firstly added into water without TSS before low activated carbon dose of 5 mg/L, caffeine removal dropped from 26% to 5%. Conversely, when TSS were present in the water sample, the removal of caffeine was not hindered under the same PAC dose and dosing sequence. The importance of the process optimisation related to removal of organic micropollutans of different hydrophilicity has been shown in this paper. Removal of around 30% of COD regardless of the dosing sequence was achieved.

Modelling and efficiency evaluation of the continuous biosorption of Cu(II) and Cr(VI) from water by agricultural waste materials.

As a result of intensive anthropogenic activities, population growth and unplanned urbanization, enormous quantities of organic and inorganic pollutants are discharged into the environment every year. The primary hazardous substances of concern regarding their environmental load and health effects are heavy metals. Heavy metal pollution of aquatic ecosystems, including resources of drinking water and water intended for food processing, has been of increasing interest. Biosorption technology is a promising strategy, as it utilizes industrial or agricultural wastes to remove metals from aqueous media passively, and they represent efficient, cost-effective and environmentally friendly alternatives to traditional adsorbents such as activated carbon. In this paper, the efficiency of biosorption of copper and chromium ions was examined using different agricultural waste biomass - sugar beet shreds, poplar sawdust and wheat straw. The possibility of applying a parallel sigmoidal (PS) model to describe the biosorption process was investigated to confirm its applicability to different types of biomass and various kinds of heavy metal ions. The results showed that the biosorption of copper ions using poplar sawdust and wheat straw consist of two steps. The moiety of one step in the overall process, defined by the parameter p, was determined to be 0.85 for poplar sawdust and 0.86 for wheat straw. These values, being less than 1, clearly indicate that the process consists of two simultaneous, kinetically different steps that shift in their dominance over the process and thus could be successfully modelled by the PS model. These studies also deal with the phenomenological examination of an unusual breakthrough curve obtained for the chromium ions biosorption by sugar beet shreds, by the comparative view of the process flow and changing the pH of the effluent. The clarification of the appearance of a double curve with a negative trend in one part allows adjusting the biosorption conditions to avoid the initial blockage of chromium ion binding to the adsorbent and thus increase the adsorption process efficiency.

Fate of natural organic matter and oxidation/disinfection by-products formation at a full-scale drinking water treatment plant.

This paper investigates the fate of natural organic matter (NOM) during the full-scale drinking water treatment plant supplied by Danube river bank filtration. After the recent reconstruction of the plant, special attention was devoted to the effects of ozone dose and granulated activated carbon (GAC) filtration on the formation and behaviour of oxidation by-products (carbonyl compounds and bromate), as well as carbonaceous and nitrogenous chlorination by-products. For the oxidation of aromatic NOM moieties that absorb light at UV254, a lower ozone dose (1.0 g O3/m3) is sufficient, whereas to achieve a measurable reduction (about 20%) of total organic carbon, an ozone dose of 1.5 g O3/m3 is required. The content of carbonyl compounds in the water after ozonation increases relative to the content before oxidation treatment, and is up to 12 times higher in the case of aldehydes and up to 2 times higher in the case of carboxylic acids. Seasonal variations, including changes in temperature and the amount of precipitation, were also shown to affect the content of organic matter in the raw water, with slight effects on the quality of the treated water. In the winter, the organic matter content is slightly higher, meaning their transformation products aldehydes and carboxylic acids, are also higher during the winter than the summer.

A new approach for modelling and optimization of Cu(II) biosorption from aqueous solutions using sugar beet shreds in a fixed-bed column.

The potential use of sugar beet shreds for copper ions removal from aqueous solution in a fixed-bed column was investigated. Experiments were performed using Box-Behnken experimental design on three levels and three variables: concentration of the inlet solution (50-150 mg L-1), adsorbent dosage (8-12 g) and pH of the inlet solution (4.0-5.0). The obtained breakthrough curves were fitted with two common empirical models, Bohart-Adams and dose-response. Observing the asymmetric shape of the breakthrough curves, the new mathematical model was proposed. The new model proposes the breakthrough curve composed of two parts, sum of which gives the asymmetrical S-shaped curve, accurately matching experimental data. Regarding the lowest SSer (7.8·10-4) and highest R2 (0.9998), new model exhibited the best fit comparing to the commonly used models. RSM and ANN modelling were employed for process variables evaluation and optimization. The most influential parameter exhibiting negative influence on target response (critical time) was concentration of the inlet solution, while the adsorbent dosage exhibited positive influence. Optimization procedure revealed that the highest critical time (341.4 min) was achieved at following conditions: C0 = 50 mg·L-1, ma = 12 g and pH 4.53 by ANN, while RSM considered pH as insignificant factor and obtained 314.8 min as the highest response.

Proteins from common bean (Phaseolus vulgaris) seed as a natural coagulant for potential application in water turbidity removal.

The ability of coagulation active proteins from common bean (Phaseolus vulgaris) seed for the removal of water turbidity was studied. Partial purification of protein coagulant was performed by precipitation with ammonium sulphate, dialysis and anion exchange chromatography. Adsorption parameters for ion-exchange process were established using dialysate extract. Results revealed that the highest values of the adsorbed protein were achieved in 50 mmol/L phosphate buffer at pH 7.5 and the maximum adsorption capacity was calculated to be 0.51 mg protein/mL matrix. Partially purified coagulant at initial turbidity 35 NTU expressed the highest value of coagulation activity, 72.3%, which was almost 22 times higher than those obtained by crude extract considering applied dosages. At the same time, the increase in organic matter that remained in water after coagulation with purified protein coagulant was more than 16 times lower than those with crude extract, relatively to its content in blank.

Removal of water turbidity by natural coagulants obtained from chestnut and acorn.

The ability of seed extracts of several species of chestnut and acorn to act as natural coagulants was tested using a synthetic turbid water. Active components were extracted from ground seeds of Horse chestnut and acorns of some species of family Fagaceae: Common oak, Turkey oak, Northern red oak and European chestnut. All investigated extracts had coagulation capabilities and their amounts depended on pH values and initial turbidities. The seed extracts from European chestnut and Common oak acorn were the most efficient expressing the highest coagulation activities, about 80% and 70%, respectively, in both low and medium investigated water turbidities at the lowest coagulant dose 0.5 ml/L.

Adsorption of heavy metals from electroplating wastewater by wood sawdust.

Poplar wood sawdust was examined for adsorption as a replacement for current, more expensive methods of removing copper, zinc and cadmium from electroplating wastewater. Langmuir, Freundlich, BET and competitive Langmuir (two competing ions) isotherms were fitted to experimental data and the goodness of their fit for adsorption was compared. The shapes of isotherms obtained fitted well with multilayer adsorption. This was established and confirmed through solid correspondence between the BET equation and experimental data, in contrast to an observed monolayer adsorption of metal ions on poplar sawdust in single metal-water solutions. The adsorption of copper ions from a mixture (in wastewater) was better than that from a single metal solution. The adsorptions of zinc ions from wastewater and from model water were approximately equal, while that of cadmium ions was significantly lower from the wastewater than from model water. The aforementioned suggests that the presence of other ions in wastewater hindered adsorption of cadmium ions.

Modified softwood sawdust as adsorbent of heavy metal ions from water.

The sawdust of deciduous softwood-poplar, and coniferous softwood-fir, have been found to possess some adsorption capacities for heavy metal ions. Their adsorption capacities can be increased by previous treatment with a sodium hydroxide solution. Adsorption capacities of alkali modified adsorbents were higher than for unmodified ones from 2.5 to 5 times for copper ions, and about 15 times for zinc ions. Also, for modification can be used solution of sodium carbonate, but that alkaline solution is less efficient than sodium hydroxide solution. The 1% sodium hydroxide solution is suggested for modification of softwood sawdust. It was established that the ion exchange is not only adsorption mechanism, than microprecipitation of metal-hydroxide in the pore liquid was happened, too. At the same time, the leaching of organic matters from modified softwood sawdust were less than from unmodified ones for about 7% for poplar and 23% for fir.