Zygmunt Mariusz Gusiatin

Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin

The influence of multiple saponin washing on copper, cadmium and zinc removal and stability in three types of soils (loamy sand, loam, silty clay) was investigated. Distribution of metals and their mobility measured as the ratio of exchangeable form to the sum of all fractions in soils was differential. After single washing the highest efficiency of metal removal was obtained in loamy sand (82-90%) and loam (67-88%), whereas the lowest in silty clay (39-62%). In loamy sand and loam metals had higher mobility factors (44-61% Cu, 60-76% Cd, and 68-84% Zn) compared to silty clay (9% Cu, 28% Cd and 36% Zn). Triplicate washing led to increase both efficiency of metal removal and percentage content of their stable forms. In consequence, fractional patterns for metals before and after treatment changed visibly as a result of their redistribution. Based on the redistribution index, the most stable metal (mainly in residual and organic fractions) after triplicate washing was Cu in loamy sand and loam. For silty clay contaminated with Cd, effective metal removal and its stabilization required a higher number of washings.

Feasibility of using humic substances from compost to remove heavy metals (Cd, Cu, Ni, Pb, Zn) from contaminated soil aged for different periods of time

There is a need for inexpensive, readily-available and environmentally-friendly soil washing agents to remediate polluted soils. Thus, batch washing experiments were performed to evaluate the feasibility of using a solution of humic substances (HS) extracted from compost as a washing agent for simultaneous removal of Cu, Cd, Zn, Pb and Ni from artificially contaminated soils aged for 1 month, 12 months and 24 months. The efficiency of metal removal in single and multiple washings and kinetic constants (equilibrium metal concentration qe and rate constant k from the second-order kinetic equation) were determined. On average, triple washing removed twice as much metal as that removed with a single washing. At pH 7 and a HS concentration of 2.2 g C L(-1), metal removal from all soils decreased in this order: Cd (79.1-82.6%) > Cu (51.5-71.8%) > Pb (44.8-47.6%) > Ni (35.4-46.1%) > Zn (27.9-35.8%). However, based on qe (mg kg(-1)), metal removal was in this order: Pb > Zn ≈ Cu > Ni > Cd. This difference was due to different concentrations of metals, which is typical for multi-metal contaminated soils. Regardless of washing mode, removal of Cd and Pb was not affected by soil age, whereas removal of Cu, Ni and Zn was higher in soils that had been aged for a shorter time. These results indicate that HS are suitable for remediating soil contaminated with multiple heavy metals in extremely high concentrations.

Humic substances from sewage sludge compost as washing agent effectively remove Cu and Cd from soil

Although commercially available biosurfactants are environmentally friendly and effectively remove heavy metals from soil, they are costly. Therefore, this study investigated whether inexpensive humic substances (HS) from sewage sludge compost could effectively remove copper (Cu) and cadmium (Cd) from highly contaminated sandy clay loam (S1) and clay (S2). The optimum HS concentration and pH were determined, as well process kinetics. Under optimum conditions, a single washing removed 80.7% of Cu and 69.1% of Cd from S1, and 53.2% and 36.5%, respectively, from S2. Triple washing increased removal from S1 to almost 100% for both metals, and to 83.2% of Cu and 88.9% of Cd from S2. Triple washing lowered the potential ecological risk (Er(i)) of the soils, especially the risk from Cd. HS substances show potential for treating soils highly contaminated with heavy metals, and HS from other sources should be tested with these and other contaminants.

Sewage sludge composting in a two-stage system: carbon and nitrogen transformations and potential ecological risk assessment.

The study examined how aeration rate (AR) in bioreactor (1.0 and 0.5l/min kg dm) at low C/N ratio (ca. 15-16) affected kinetics of organic matter (OM) removal, i.e. rate constant of OM removal (k) and maximum degradation of OM (A) and nitrogen evolution during sewage sludge composting. Moreover, potential ecological risk (Er) based on metal (Cd, Cr, Cu, Hg, Ni, Pb, Zn) content was evaluated. The process involved a two-stage system (bioreactor and windrow). In the bioreactor, at higher AR, k and A equaled 0.34 d(-1) and 101.9 g/kg dm, respectively; at lower AR k was 0.38 d(-1), however A 1.4-fold lower. Interestingly, in the windrow, k was much higher (0.086 d(-1)) for the biomass subjected to a lower AR, compared to 0.026 d(-1) at higher AR. Moreover, although at lower AR, k in the windrow was 4.4-fold lower than in the bioreactor, A was 1.15-fold higher. Total N content in mature compost was on the level 23.51-22.35 g/kg dm and metal concentration showed low ecological risk (Er < 16).

Tannic acid and saponin for removing arsenic from brownfield soils: Mobilization, distribution and speciation

Plant biosurfactants were used for the first time to remove As and co-existing metals from brownfield soils. Tannic acid (TA), a polyphenol, and saponin (SAP), a glycoside were tested. The soil washing experiments were performed in batch conditions at constant biosurfactant concentration (3%). Both biosurfactants differed in natural pH, surface tension, critical micelle concentration and content of functional groups. After a single washing, TA (pH 3.44) more efficiently mobilized As than SAP (pH 5.44). When both biosurfactants were used at the same pH (SAP adjusted to 3.44), arsenic mobilization was improved by triple washing. The process efficiency for TA and SAP was similar, and depending on the soil sample, ranged between 50%-64%. Arsenic mobilization by TA and SAP resulted mainly from decomposition of Fe arsenates, followed by Fe(3+) complexation with biosurfactants. Arsenic was efficiently released from reducible and partially from residual fractions. In all soils, As(V) was almost completely removed, whereas content of As(III) was decreased by 37%-73%. SAP and TA might be used potentially to remove As from contaminated soils.

Semi-continuous anaerobic digestion of different silage crops: VFAs formation, methane yield from fiber and non-fiber components and digestate composition

This study presents the results of long-term semi-continuous experiments on anaerobic digestion at an HRT of 45d with ten silages: 2 annual and 4 perennial crops, and 4 mixtures of annual with perennial crops. The composition of substrates and digestates was determined with Van Soests fractionation method. Removal of non-fiber materials ranged from 49.4% (Miscanthus sacchariflorus) to 89.3% (Zea mays alone and mixed with M. sacchariflorus), that of fiber materials like lignin ranged from 0.005% (Z. mays alone and mixed with grasses at VS ratio of 90:10%) to 46.5% (Sida hermaphrodita). The lowest stability of anaerobic digestion, as confirmed by normalized data concentrations of volatile fatty acids, was reported for both miscanthuses and sugar sorghum. The methane yield coefficients for non-fiber and fiber materials were 0.3666 and 0.2556L/g, respectively. All digestate residues had high fertilizing value, especially those from mixtures of crops.

The usability of the IR, RAC and MRI indices of heavy metal distribution to assess the environmental quality of sewage sludge composts

To assess the environmental quality of compost, it is insufficient to use only total metal concentration. Therefore in this study, the stability of metals in compost and the environmental risk they pose were assessed by three indices that have been proposed for soils or sediments: the IR, the RAC and the MRI. In mature composts, the highest bonding intensity was for Ni (0.79<IR<0.93), then for Cu (0.56<IR<0.65) and Pb (0.55<IR<0.73), and the lowest for Zn (0.19<IR<0.25). Although, both the IR and the RAC are useful indices for evaluating the mobility of metals, they do not take into account their toxicity. Therefore, the overall classification of compost should also include the MRI, at which metal toxicity from the most available fractions is considered. Based on the MRI ranged between 10.0 and 11.6, all composts evaluated posed a low risk.

Behaviors of heavy metals (Cd, Cu, Ni, Pb and Zn) in soil amended with composts

ABSTRACT This study investigated how amendment with sewage sludge compost of different maturation times (3, 6, 12 months) affected metal (Cd, Cu, Ni, Pb, Zn) bioavailability, fractionation and redistribution in highly contaminated sandy clay soil. Metal transformations during long-term soil stabilization (35 months) were determined. In the contaminated soil, Cd, Ni and Zn were predominately in the exchangeable and reducible fractions, Pb in the reducible fraction and Cu in the reducible, exchangeable and oxidizable fractions. All composts decreased the bioavailability of Cd, Ni and Zn for up to 24 months, which indicates that cyclic amendment with compost is necessary. The bioavailability of Pb and Cu was not affected by compost amendment. Based on the reduced partition index (IR), metal stability in amended soil after 35 months of stabilization was in the following order: Cu > Ni = Pb > Zn > Cd. All composts were more effective in decreasing Cd, Ni and Zn bioavailability than in redistributing the metals, and increasing Cu redistribution more than that of Pb. Thus, sewage sludge compost of as little as 3 months maturation can be used for cyclic amendment of multi-metal-contaminated soil.

ADM1-based modeling of anaerobic codigestion of maize silage and cattle manure – a feedstock characterisation for model implementation (part I) / Modelowanie kofermentacji kiszonki kukurydzy i obornika bydlęcego za pomocą ADM1 – charakterystyka wsadu surowcowego (część I)

Abstract This paper presents the results of fractionation of particulate and soluble organic matter in a mixture of maize silage and cattle manure (49:51% volatile solids) that was used as a feedstock for anaerobic digestion. The extended Weender’s analysis was adapted to measure raw protein, raw lipids, fraction of carbohydrates (including starch, cellulose, hemicelluloses) and lignin. The content of individual fractions in composite, Xc (as kg COD kg-1 COD) was: 0.111 proteins, 0.048 lipids, 0.500 carbohydrates and 0.341 inerts. The biodegradability of Xc was 68%. Based on material balance, the carbon concentration in Xc was 0.0326 kmol C kg-1 COD, whereas nitrogen concentration 0.0018 kmol N kg-1 COD. The estimated pH of the feedstock based on acid-base equilibrium corresponded to the actual value (pH 7.14). Streszczenie W pracy przedstawiono wyniki stężenia substancji chemicznych rozpuszczonych i nierozpuszczonych w mieszaninie kiszonki kukurydzy zwyczajnej i obornika bydlęcego (49:51% suchej masy organicznej), który wykorzystano jako substrat do wytwarzania biogazu. Do frakcjonowania nierozpuszczalnych związków organicznych, stanowiących kompozyt (Xc), wykorzystano metodę Weender’a. Udział poszczególnych frakcji (jako ChZT) w kompozycie wyniósł: białka - 0,111, tłuszcze - 0,048, węglowodany - 0,500 oraz związki inertne - 0,341. Stężenie związków biodegradowalnych w kompozycie wyniosło 68%. Na podstawie bilansu materiałowego węgla i azotu obliczono, że stężenie węgla w kompozycie wynosi 0,0326 kmol C kg-1 ChZT, zaś azotu 0,0018 kmol N kg-1 ChZT. Odczyn (pH) wsadu surowcowego wyznaczony z równowagi kwasowo-zasadowej odpowiadał rzeczywistemu, tj. 7,14.

ADM1-based modeling of anaerobic codigestion of maize silage and cattle manure – calibration of parameters and model verification (part II) / Modelowanie kofermentacji kiszonki kukurydzy i obornika bydlęcego za pomocą ADM1 – kalibracja i weryfikacja modelu (część II)

Abstract The aim of this study was to implement ADM1xp model to simulate behavior of anaerobic co-digestion of maize silage and cattle manure. The accuracy of ADM1xp has been assessed against experimental data of anaerobic digestion, performed at OLR = 2.1 gVS dm-3·d-1 and HRT = 45d. Due to the high number of parameters in ADM1xp, it was necessary to develop a customized procedure limiting the range of parameters to be estimated. The best fitting of experimental to simulated data was obtained after verification of 9 among 105 stoichiometric and kinetic parameters. The values of objective function (Jc) ranged between 0.003 (for valerate) and 211 (for biogas production). Streszczenie Celem pracy było wykorzystanie modelu ADM1xp do symulacji procesu kofermentacji kiszonki kukurydzy i obornika bydlęcego. Przydatność modelu oceniano wykorzystując dane z eksperymentu w skali laboratoryjnej. Badania prowadzono przy obciążeniu komory ładunkiem organicznym OLR = 2,1 gVS dm-3·d-1 oraz hydraulicznym czasie zatrzymania wsadu w fermentorze, HRT = 45d. Z powodu dużej liczby parametrów w modelu ADM1xp, zastosowano procedurę, która umożliwia zmniejszenie liczby weryfi kowanych parametrów podczas kalibracji. Najlepsze dopasowanie danych eksperymentalnych do modelowych uzyskano po weryfikacji 9 spośród 105 stechiometrycznych i kinetycznych parametrów. Wartości współczynnika dopasowania (Jc) zmieniały się w zakresie od 0,003 (kwas walerianowy) do 211 (produkcja biogazu).