Giovanni Gigliotti

Long-term distribution, mobility and plant availability of compost-derived heavy metals in a landfill covering soil

The application of municipal waste compost (MWC) and other organic materials may serve to enhance soil fertility of earthen materials and mine spoils used in land reclamation activities, particularly in the recovery of degraded areas left by exhausted quarries, mines and landfill sites among others. The long-term distribution, mobility and phytoavailability of heavy metals in such anthropogenic soils were studied by collecting soil samples at different depths over a 10 y chronosequence subsequent to amendment of the top layer of a landfill covering soil with a single dose of mechanically-separated MWC. Amendment resulted in a significant enhancement of the metal loadings in the amended topsoils particularly for Cu, Zn and Pb, which were also the predominant metals in the compost utilised. Although metals were predominantly retained in the compost amended soil horizon, with time their vertical distribution resulted in a moderate enrichment of the underlying mineral horizons, not directly influenced by compost amendment. This enrichment generally resulted from the leaching of soluble organo-metal complexes and subsequent adsorption to mineral horizons. However, in the course of the 10-y experimental period, metal concentrations in the underlying horizons generally returned to background concentrations suggesting a potential loss of metals from the soil system. Analysis of the tissues of plants growing spontaneously on the landfill site suggests that metal phytoavailability was limited and generally species-dependent.

Respiration Index Determination: A Comparative Study of Different Methods

Three respirometric methods were tested using 18 organic matrices. Two methods were performed in the solid state condition using static (SRI) and dynamic approaches (DRI) while the third was performed in the liquid state (SOUR). The results obtained showed that all methods were able to describe biological stability and were well correlated. SOUR gave results that differed from DRI and SRI, which, in turn, showed good agreement. SOUR showed a good correlation with dissolved organic carbon, above all with the hydrophilic fraction, indicating that water media was responsible for the high availability of soluble organic material during initial hours of the test. The use of SOUR cumulative data (OD12 and OD20) reduced the effect of the soluble fraction on the measurement, thereby increasing the correlation coefficient with the solid state methods.

Differences in the chemical composition of dissolved organic matter from waste material of different sources

Abstract. The chemical composition of waste-material-derived dissolved organic matter (DOM) was characterized by chemolytic analyses and 1H, 13C and 31P nuclear magnetic resonance (NMR) spectroscopy. Dissolved organic matter was extracted by water from an aerobic fermented urban waste compost, a sewage sludge and a pig slurry and then fractionated using the XAD-8 method. The amount of water-extractable dissolved organic carbon (DOC) ranged from 3% in the sewage sludge to 22% in the pig slurry. Dissolved organic matter isolated from pig slurry was equally distributed between hydrophilic and hydrophobic DOC, whereas in the sewage-sludge-derived material the hydrophobic fraction was predominant. Dissolved organic C from the urban waste compost was mainly within the hydrophilic fraction. Wet-chemical analysis and 1H- and 13C-NMR spectra showed that both DOM fractions from the urban waste compost were low in neutral, acidic and amino sugars as well as in lignin-derived compounds. In turn, the materials were rich in low-molecular-weight aliphatic compounds. The chemical structure of both fractions is probably the result of the intensive transformation of urban waste compost during its fermentation. The hydrophilic fractions of DOM from sewage sludge and pig slurry contained considerable amounts of carbohydrates but were also rich in low-molecular-weight aliphatics. The respective hydrophobic fractions had the largest contents of CuO-extractable phenols which may in part derive from sources other than lignin. By contrast with the other materials, the hydrophobic fraction from the pig slurry seemed to contain polymeric rather than low-molecular-weight material. The 31P-NMR spectrum of the hydrophilic DOM fraction from urban waste compost did not show signals of inorganic or organic P compounds while the spectrum of the hydrophobic fraction revealed traces of monoester P, diester P, and orthophosphate. 31P-NMR spectroscopy suggested that both the hydrophobic and hydrophilic fractions from pig slurry did not contain organic P. The hydrophilic DOM fraction from sewage sludge contained orthophosphate, organic monoester P and a little pyrophosphate. The hydrophobic fraction contained mainly organic diester P and smaller amounts of teichoic acids and organic monoester P. Considering that water-soluble fractions of urban waste compost contained no easily plant-available P and a low content of labile organics, we conclude that this material contains less labile nutrients and is more refractory than the soluble constituents of pig slurry and sewage sludge.

Trace metals uptake and distribution in corn plants grown on a 6-year urban waste compost amended soil

A 6-year field study was performed to evaluate heavy metal accumulation in the top 20 cm of a clay-loam calcareous soil (Fluventic Xerochrept) amended with urban waste compost and to determine heavy metal uptake and distribution in corn plants grown in this soil. Compared with untreated soils, amended soils showed a significant increase only in Cu, Zn, Pb and, in the last 2 years, Cr concentrations. The corn plants grown on the amended soil showed a general increase in metal uptake, which was about three times greater for Pb and two times greater for the other heavy metals than in plants grown on untreated soil. At times, the diluting effect resulting from enhanced growth rates of the plants with compost application resulted in lower concentrations in the plants grown on treated plots. Cr and Pb were less mobile in the corn plant and were accumulated only in root tissues. Only in the last 3 years of the experiment were traces of Pb found also in the stalks. The limited mobility of Pb was confirmed in a contemporary hydroponic greenhouse experiment. The values of the plant/soil transfer coefficients were within the lower range reported in the literature, indicating that in the soil studied (which contained 14% CaCO3) there was limited transfer of heavy metal ions from the soil to the corn plants. It is concluded that the long-term application of large amounts of urban waste compost to CaCO3-containing soils does not necessarily cause medium-term problems to plant, animal or human health.

Composition changes of dissolved organic matter in a soil amended with municipal waste compost

A spectroscopic study was carried out to determine the changes in composition of dissolved organic matter (DOM) in a soil repeatedly amended with a municipal waste compost. In addition to humic-like substances, composted products contain dissolved organic matter composed ofa complex mixture of relatively low molecular weight polymeric materials. The FT-IR and 1 H-NMR spectra of DOM extracted from a clay-loam soil (SDOM), municipal waste compost (CDOM), and soil-compost mixtures incubated for varying time periods are reported. One ofthe incubated samples was taken from a freshly prepared laboratory mixture (LASDOM); the rest were taken from a 6-year field experiment on the soil collected at four months (6YASDOM) after the last amendment. The analyses were carried out also on a CDOM sample after being kept in contact with the soil for 24 h (BEER). The main findings ofthe IR and 1 H-NMR spectra concern polysaccharides and olefinic groups. The former increased in concentration in both 6YASDOM (vs. SDOM and LASDOM), and BEER (vs. CDOM). The 6YASDOM finding proves that the increase in polysaccharides was caused by the evolution of the added municipal waste compost rather than by a direct addition of the compost. The polysaccharide increase in BEER testifies to a selective adsorption by the soil of humus-like organic macromolecules containing COOH groups, thereby increasing the concentration of the less adsorbed hydrophilic polysaccharide molecules, which would also explain the increase in polysaccharides in the 6YASDOM. Conversely, the concentration of olefinic groups was high in SDOM and low in CDOM, LASDOM, and BEER. This finding supports the hypothesis that the highly reactive olefinic groups present in SDOM react rapidly with CDOM molecules, thus lowering their concentration. In conclusion, compared with soil DOM, the increase of polysaccharides and the decrease of olefinic groups seem to be the most important characteristic of DOM in soils amended with municipal waste compost.

Chemical and spectroscopic characterization of organic matter during the anaerobic digestion and successive composting of pig slurry

In this work, anaerobic digestion of pig slurry and successive composting of the digestate after centrifugation were studied by means of chemical analysis, FTIR and fluorescence spectroscopy as excitation-emission matrix (EEM). Chemical analysis highlighted the organic matter transformation occurring during the processes. A decrease of volatile solids and total organic carbon were observed in the digestate with respect to the fresh pig slurry as a consequence of the consumption of sugars, proteins, amino acids and fatty acids used by microorganisms as a C source. Water Extractable Organic Matter (WEOM) was obtained for all samples and fractionated into a hydrophilic and a hydrophobic fraction. The highest WEOM value was found in the pig slurry indicating a high content of labile organic C. The digestate centrifuged and the digestate composted showed lower hydrophilic and higher hydrophobic contents because of the decrease of labile C. Total phenolic content was lower in the digestate with respect to fresh pig slurry sample (36.7%) as a consequence of phenolic compounds degradation. The strong decrease of total reducing sugars in the digestate (76.6%) as compared to pig slurry confirmed that anaerobic process proceed mainly through consumption of sugars which represent a readily available energy source for microbial activity. FTIR spectra of pig slurry showed bands indicative of proteins and carbohydrates. A drop of aliphatic structures and a decrease of polysaccharides was observed after the anaerobic process along with the increase of the peak in the aromatic region. The composted substrate showed an increase of aromatic and a relative decrease of polysaccharides. EEM spectra provided tryptophan:fulvic-like fluorescence ratios which increased from fresh substrate to digestate because of the OM decompostion. Composted substrate presented the lowest ratio due to the humification process.

Long-term effects of heavy metals from composted municipal waste on some enzyme activities in a cultivated soil

A 3-year field experiment on a calcareous Fluventic Xerochrept planted with corn (Zea mays L.) was carried out to evaluate the effects of amending the soil with high and low rates of composted municipal waste on soil enzyme activities (alkaline phosphomonoesterase, phosphodiesterase, arylsulphatase, dehydrogenase, and l-asparaginase). These enzyme activities all increased when compost was added at rates of up to 90 t ha-1, and the phosphatases continued to show a linear increase with compost rates of up to 270 t ha-1. The addition of mineral fertilizer increased enzyme activities in unamended soil, and masked the stimulating effect of compost on the amended soils. Heavy metals did not affect soil enzyme activities up to a compost addition of at least three times the amount specified by Italian law.

Co-treatment of fruit and vegetable waste in sludge digesters. An analysis of the relationship among bio-methane generation, process stability and digestate phytotoxicity.

The co-digestion of a variable amount of fruit and vegetable waste in a waste mixed sludge digester was investigated using a pilot scale apparatus. The organic loading rate (OLR) was increased from 1.46 kg VS/m(3) day to 2.8 kg VS/m(3) day. The hydraulic retention time was reduced from 14 days to about 10 days. Specific bio-methane production increased from about 90 NL/kg VS to the maximum value of about 430 NL/kg VS when OLR was increased from 1.46 kg VS/m(3) day to 2.1 kg VS/m(3) day. A higher OLR caused an excessive reduction in the hydraulic retention time, enhancing microorganism wash out. Process stability evaluated by the total volatile fatty acids concentration (mg/l) to the alkalinity buffer capacity (eq. mg/l CaCO3) ratio (i.e. FOS/TAC) criterion was <0.1 indicating high stability for OLR <2.46 kg VS/m(3 )day. For higher OLR, FOS/TAC increased rapidly. Residual phytotoxicty of the digestate evaluated by the germination index (GI) (%) was quite constant for OLR<2.46 kg VS/m(3)day, which is lower than the 60% limit, indicating an acceptable toxicity level for crops. For OLR>2.46 kg VS/m(3) day, GI decreased rapidly. This corresponding trend between FOS/TAC and GI was further investigated by the definition of the GI ratio (GIR) parameter. Comparison between GIR and FOS/TAC suggests that GI could be a suitable criterion for evaluating process stability.

Hybrid solid anaerobic digestion batch: biomethane production and mass recovery from the organic fraction of solid waste

An experimental apparatus was constructed to perform hybrid solid anaerobic digestion batch processing of the organic fraction of municipal solid waste. The preliminary process was carried out with a high total solids concentration of about 33% w w−1 and with an initial organic load of about 340 kg VS kg−1. The fresh organic fraction to inoculum ratio used to enhance the anaerobic process start-up was 0.910 kg VS kg VS−1. The process was conducted by spreading the percolate on top of the mixture. The percolate was stored in a separate section of the apparatus with a mean hydraulic retention time of about 1 day. During the process, acetate, butyrate and propionate in the percolate reached concentrations ranging from 3000 to 11 000 mg L−1. In spite of these high concentrations, the biomethane produced from both the solid and the percolate was quite high, at about 210 NL kg VS−1. The digestate obtained at the end of the run showed rather good features for being classified as an organic fertilizer according to Italian law. However, a residual phytotoxicity level was detected by a standardized test showing a germination index of about 50%.

Composition changes of soil humus after massive application of urban waste compost: a comparison between FT-IR spectroscopy and humification parameters

A laboratory trial and a six-year field experiment were carried out to evaluate the changes in the composition of humic substances in a soil amended for six years with urban waste compost (UWC), and to compare the results obtained by FT-IR spectroscopy with empirical humification parameters. The fulvic acid FT-IR spectra showed that amended soils contain a higher concentration of carboxylic and aliphatic groups compared to unamended soil (UNAS). The six-year amended soil (SYAS) also showed a higher content of polysaccharides on FT-IR spectra of both humic and fulvic acids. The polysaccharide increase in the six-year amended soil is attributable to the humification process since polysaccharides were not present in a high quantity in the UWC or laboratory amended soil (LAAS). The humification index and the degree of humification values indicate that the urban waste compost and soils studied can be classified in decreasing order of humification as follows: UNAS > SYAS > LAAS > UWC. This behaviour is the consequence of an increasing presence of the non humified fraction in NaOH extracted organic matter. The carboxylic and aliphatic groups content from FT-IR spectra confirmed this behaviour, thus indicating the validity of the humification parameters used to evaluate the status of the organic matter from refuse and soil.