An IR study to investigate the structural relationship of lignin-like matter and lignosulphonates obtained from animal-vegetable wastes

Lignin-like matter (I) from rice hull residues and humin-like matter and (II) from rice hull-fecal matter compost yield, upon sulphonation by SO(3), the lignosulphonates III and IV, respectively. The solid state IR spectra of I and II are analysed and interpreted based on the functional groups content values obtained for III and IV by solution NMR spectroscopy. IR absorbance values at five selected wavelengths for I and II correlate well with functional groups content values for III and IV according to Beer's law. It is concluded that the sulphonated derivatives, aside from the -SO(3)H content, reflect well the chemical structure of the parent materials. No side reaction of I or II with SO(3), other than C sulphonation, is apparent. The above correlation may be useful for waste management purposes.     

Polyalkylphenyl-sulphonic acid with acid groups of variable strength from compost

The insoluble organic fraction (humin-like material, HLM) from rice hull-dairy cattle compost is well converted into water soluble HLM-sulphonate by reaction in liquid SO3. Microanalytical, potentiometric, molecular weight, and NMR data are consistent with a highly homogeneous polymeric arylsulphonate having 4000 Da MW, 1.3 sulphonic groups per aromatic ring and significant content of carboxylic and phenolic groups. By comparison with structure-property relationships for commercial lignosulphonates derived from the pulp and paper industry, the above arylsulphonate is likely to be a candidate at a variety of applications in the chemical industry and in agriculture. Therefore, sulphonation is a means for upgrading composts HLM to the same uses as for commercial lignosulphonates.     

The mineralisation of fresh and humified soil organic matter by the soil microbial biomass

Soil organic matter comprises all dead plant and animal residues, from the most recent inputs to the most intensively humified. We have found that traces of fresh substrates at microg g(-1) soil concentrations (termed 'trigger molecules') activate the biomass to expend more energy than is contained in the original 'trigger molecules'. In contrast, we suggest that the rate limiting step in soil organic matter mineralisation is independent of microbial activity, but is governed by abiological processes (which we term the Regulatory Gate theory). These two findings have important implications for our understanding of carbon mineralisation in soil, a fundamental process in the sequestration of soil organic matter.     

Agrochemical characterisation of the solid by-products and residues from the winery and distillery industry

The winery and distillery industry produces a great quantity of residues, whose management and disposal are environmental problems due to their seasonal character and some polluting characteristics. The main solid by-products and residues generated are grape stalk, grape pomace or marc, wine lee, exhausted grape marc and winery sludge. In this study, 87 samples of winery and distillery residues were collected from different Spanish wineries and distilleries. Electrical conductivity, pH, total organic matter, organic carbon, polyphenols and contents of plant nutrients and heavy metals were determined. The purpose of this research was to study the composition of these wastes and to find relationships in order to use easily analysable parameters to estimate their composition. In general, the winery and distillery residues showed low pH (mean values ranged from 3.8 to 6.8) and electrical conductivity values (1.62-6.15 dS m(-1)) and high organic matter (669-920 g kg(-1)) and macronutrient contents, especially in K (11.9-72.8 g kg(-1)). However, a notable polyphenol concentration (1.2-19.0 g kg(-1)) and low micronutrient and heavy metal contents were also observed, some of these properties being incompatible with agricultural requirements. Therefore, conditioning treatments are necessary prior to possible use of these wastes. In all wastes, significant correlations were found between easily determined parameters, such as pH, electrical conductivity and total organic matter, and most of the parameters studied. The regression models obtained are also discussed.     

Change of the chemical composition and biodegradability of the Van Soest soluble fraction during composting: A study using a novel extraction method

Van Soest fractionation is widely employed to characterize exogenous organic matter. The soluble fraction of Van Soest fractionation (SOL, extracted using hot water and then neutral detergent) often increases in line with compost maturity, although it is generally considered as labile. We have developed an alternative extraction method that comprises four successive steps (extraction using hot water, sodium tetraborate, dichloromethane/methanol and chelating resin) in order to clarify the chemical nature of the SOL fraction and explain its biodegradability. This method was tested on municipal solid waste compost sampled during the thermophilic phase (MSWi) and after 8 months of composting (MSWm). Both methods extracted similar proportions of organic matter. The composition of the residues was similar in MSWm although differences were noted for the extraction of polysaccharides and lipids in the case of MSWi. The hot water extractable fraction decreased during composting. Its high biodegradability in MSWi was linked to the high polysaccharide content revealed by pyrolysis–GC/MS and FTIR spectroscopy. The increase in the sodium tetraborate extractable fraction mainly explained the increase in the SOL fraction during composting. This was made up of N-containing compounds, polysaccharides and lipids in the immature compost, and a majority of N-containing compounds in the mature compost. During composting, the stabilization of organic matter in the SOL fraction extractable by sodium tetraborate and EDTA might principally involve N-containing structures through the formation of complexes of organic matter with metal ions, especially Ca²⁺, which may be broken down during extraction of the Van Soest soluble fraction. These mechanisms still need to be investigated.     

Composting of a solid olive-mill by-product ("alperujo") and the potential of the resulting compost for cultivating pepper under commercial conditions

A pollutant solid material called "alperujo" (AL), which is the main by-product from the Spanish olive oil industry, was composted with a cotton waste as bulking agent, and the compost obtained (ALC) was compared with a cattle manure (CM) and a sewage sludge compost (SSC) for use as organic amendment on a calcareous soil. The experiment was conducted with a commercial pepper crop in a greenhouse using fertigation. Composting AL involved a relatively low level of organic matter biodegradation, an increase in pH and clear decreases in the C/N and the fat, water-soluble organic carbon and phenol contents. The resulting compost, which was rich in organic matter and free of phytotoxicity, had a high potassium and organic nitrogen content but was low in phosphorus and micronutrients. The marketable yields of pepper obtained with all three organic amendments were similar, thus confirming the composting performance of the raw AL. When CM and SSC were used for soil amendment, the soil organic matter content was significantly reduced after cultivation, while it remained almost unchanged in the ALC-amended plots.     

Modification of soil humic matter after 4 years of compost application

Two soil plots, 1 ha each, were amended yearly for 4 years, respectively, with 35.8 and 71.6 Mg ha(-1) yr(-1) of mature compost (CM) obtained from food and vegetable residues. The compost, amended soils, and a control soil plot after 4 years (S4), were analyzed for humin (HUC), humic acid (HAC), fulvic acid (FAC), and non-humic carbon (NHC) content. Compared to S4, the amended soil contained more humified C (HAC, FAC and HUC) and less NHC. Further evidence of the effect of compost on soil organic matter was obtained by the analysis of the humic acid (HA) fractions isolated from both the compost and the soils. These were characterized by elemental analyses and Diffuse Reflectance Infrared Fourier Transformed spectroscopy. The HAs isolated from CM and from S4 were significantly different. The HAs isolated from the amended plots were more similar to HA isolated from CM than to HA isolated from S4. The experimental data of this work indicate that the compost application may affect significantly the soil organic matter composition, and that the approach used in this work allows one to trace the fate of compost organic matter in soil.     

The effect of sediment redox chemistry on solubility/chemically active forms of selected metals in bottom sediment receiving produced water discharge

The effect of sediment redox conditions on the solubility behavior of Fe, Pb, Ni, Ba, and Cu in bottom sediment collected from a produce water discharge site was investigated using kinetics and chemical fractionation procedures. Sediment collected was composited and subsamples incubated in laboratory microcosms under controlled Eh-pH conditions. Sediment was sequentially extracted for determining metals in five fractions (exchangeable, carbonate, bound to iron and manganese oxide, bound to organic matter and sulfide, mineral matrix or residue). Metal distribution in the fractions indicates that under oxidizing sediment conditions, the behavior of Fe, Pb and Ni were governed by Fe(III) and Mn(IV) oxides; Ba by insoluble complexation with humic compounds; and Cu by carbonates and humic complexation. Under reducing sediment condition, the behaviors of Fe and Cu were controlled by the formation of insoluble sulfides and humic complexes; the behaviors of Ni and Ba by carbonate and Pb behavior by sulfides, carbonates and humic complexes. With increases in sediment redox potential, the affinity between Fe(III), Mn(IV) oxides and Fe, Pb, Ni, Cu increased, the affinity between insoluble large molecular humic and Ba increased, and the affinity between carbonates and Cu increased. With decreasing sediment redox potential, the affinity between carbonates and Fe, Ni, Ba increased; the affinity between sulfides, humic substances and Fe, Pb, Ni, Cu also increased. Upon Fe(III) oxide reduction, it is estimated that 20% of total reducible Fe(III) oxides was reduced by direct bacterial reduction (K = −42.6 ppm/day), 80% of total reducible Fe(III) oxides was associated with chemical fractions attributed to sulfide oxidation (K = −171.5 ppm/day). The rate constants (ppm/day) for dissolved Ni (Eh <0 mV), Pb (Eh < −80 mV) and Cu (−80 mV < Eh <0 mV) are −1.6, −0.047 and −0.16, respectively. In our incubation period, the rate constants (ppm/day) for Ni bound to Fe(III) and Mn(IV) oxides, Ba bound to carbonates and Cu bound to insoluble large molecular humic are −3.2, 0.91 and 4.3, respectively.     

Effect of organic residues addition on the technological properties of clay bricks

The objective of this study is to investigate the utilization potential of several organic residues in clay bricks. Sawdust, tobacco residues, and grass are widespread by-products of industrial and agricultural processes in Turkey. These residue materials have long cellulose fibres. Sawdust and tobacco residues generally are used as fuel, and the grass is utilized for agricultural purposes. The insulation capacity of brick increases with the increasing porosity of the clay body. Combustible, organic types of pore-forming additives are most frequently used for this purpose. For this reason, increasing amounts of organic residues (0%, 2.5%, 5% and 10% in wt.) were mixed with raw brick-clay. All samples were fired at 900 degrees C. Effects on shaping, plasticity, density, and mechanical properties were investigated. The organic residue additions were found to be effective for pore-forming in the clay body with the clay maintaining acceptable mechanical properties. It was observed that the fibrous nature of the residues did not create extrusion problems. However, higher residue addition required a higher water content to ensure the right plasticity. As a result, sawdust, tobacco residues, and grass can be utilized in an environmentally safe way as organic pore-forming agents in brick-clay.     

Composite Biofilms grown in Acidic Mining Lakes and assessed by Electron Microscopy and Molecular Techniques

Microbial consortia of composite biofilms, grown in surface water of acidicmining lakes near Lauchhammer, Germany, were investigated. The red-brown colored lake water was acidic (pH 2.5), had high concentrations of Fe(III), Al(III), and sulphate and low concentrations of dissolved organic matter. As a result the abundance of bacteria in the lake is with 10⁴ cells mL^-1 rather low. One input of organic material into the lake are autumnal leaves from trees, growing in the lakeside area. From aliquots of unfixed birch leave biofilms the 16S rRNA genes were amplified by PCR and community fingerprints were determined by single-strand conformation polymorphism (SSCP) analysis. Specific bands within the fingerprints were extracted from SSCP gels and sequenced for the taxonomical affiliation.These results were compared with those from the second type of biofilms which were grown on sterile substrata, floating submersed in surface waters of the lakes. By excising the bands from the gel and sequencing the individual bands bacterial taxa, common to both types of biofilms, were found but also some, which were only present in one type of biofilm. Ultrathin sectioned biofilms often showed bacteria associated with electron dense particles as main inorganic constituents. Elemental microanalysis by energy dispersive X-ray analysis (EDX) revealed them to contain iron, sulfur and oxygen as main elemental fractions and electron diffraction ring pattern analysis classified them to be schwertmannite. These bacteria and their interactions with each other as well as with the inorganic minerals formed in this lake generally is of great interest, in order to use these results for bioremediation applications.     

Microbial cycling of iron and sulfur in acidic coal mining lake sediments

Lakes caused by coal mining processes are characterized by low pH, low nutrient status, and high concentrations of Fe(II) and sulfate due to the oxidation of pyrite in the surrounding mine tailings. Fe(III) produced during Fe(II) oxidation precipitates to the anoxic acidic sediment, where the microbial reduction of Fe(III) is the dominant electron-accepting process for the oxidation of organic matter, apparently mediated by acidophilic Acidiphilium species. Those bacteria can reduce a great variety of Fe(III)-(hydr)oxides and reduce Fe(III) and oxygen simultaneously which might be due to the small differences in the redox potentials under low pH conditions. Due to the absence of sulfide, Fe(II) formed in the upper 6 cm of the sediment diffuses to oxic zones in the water layer where itcan be reoxidized by Acidithiobacillus species. Thus, acidic conditions are stabilized by the cycling of iron which inhibits fermentative and sulfate-reducing activities. With increasing sediment depth, the amount of reactive iron decrease, the pH increases above 5, and fermentative and as yet unknown Fe(III)-reducing bacteria are also involved in the reduction of Fe(III). Sulfate is reduced apparently by the activity of spore-forming sulfate reducers including new species of Desulfosporosinus that have their pH optimum similar to in situconditions and are not capable of growth at pH 7. However, generation of alkalinity via sulfate reduction is reduced by the anaerobic reoxidation of sulfide back to sulfate. Thus, the microbial cycling of iron at the oxic-anoxic interface and the anaerobic cycling of sulfur maintains environmental conditions appropriate for acidophilic Fe(III)-reducing and acid-tolerant sulfate-reducing microbial communities.     

EU strategies and policies on soil and waste management to offset greenhouse gas emissions

Climate change has become an important political priority in the environmental field, and beyond. To revert the increase in the Earth’s temperature, developed country parties to the Kyoto Protocol committed to limit their greenhouse gas emissions. The 15 Member States that made up the European Community in 1997 have a combined reduction target of 8% in CO₂-equivalent emissions in the period 2008–2012 compared to 1990. The role of soil, both as a source and a sink for carbon, is particularly important. How can soil organic matter be maintained or increased? There is no single answer, and a broad range of options need to be explored. Among the different measures proposed, the promotion of organic input on arable land (crop residues, cover crops, farm yard manure, compost, sewage sludge) has been mentioned. The challenge is to ensure that organic wastes of good quality are used to increase soil organic matter in carbon depleted soils and that appropriate monitoring is established. On the waste management front, the European Commission intends to produce guidance for Member States on the management of biowaste that will take into account all related environmental issues, including soil aspects. As for monitoring, the European Commission has put forward legislation according to which Member States would have to identify the areas at risk of soil organic matter decline in their national territory. Such legislation should be regarded as a major step forward for Europe, as it would ensure a high level of soil protection across the Community. This development will have the potential to enable the kind of estimation, measurement or modelling of crop or grazing land management needed for accounting under Article 3.4 of the Kyoto Protocol.     

The effects of substrate pre-treatment on anaerobic digestion systems: a review

Focus is placed on substrate pre-treatment in anaerobic digestion (AD) as a means of increasing biogas yields using today's diversified substrate sources. Current pre-treatment methods to improve AD are being examined with regard to their effects on different substrate types, highlighting approaches and associated challenges in evaluating substrate pre-treatment in AD systems and its influence on the overall system of evaluation. WWTP residues represent the substrate type that is most frequently assessed in pre-treatment studies, followed by energy crops/harvesting residues, organic fraction of municipal solid waste, organic waste from food industry and manure. The pre-treatment effects are complex and generally linked to substrate characteristics and pre-treatment mechanisms. Overall, substrates containing lignin or bacterial cells appear to be the most amendable to pre-treatment for enhancing AD. Approaches used to evaluate AD enhancement in different systems is further reviewed and challenges and opportunities for improved evaluations are identified.     

Enzymatic pretreatment of lignocellulosic wastes to improve biogas production

The effect of enzymatic pretreatment of sugar beet pulp and spent hops prior to methane fermentation was determined in this study. These industrial residues were subjected to enzymatic digestion before anaerobic fermentation because of high fiber content (of 85.1% dry matter (DM) and 57.7% DM in sugar beet pulp and spent hops, respectively). Their 24h hydrolysis with a mix of enzymatic preparations Celustar XL and Agropect pomace (3:1, v/v), with endoglucanase, xylanase and pectinase activities, was most effective. Reducing sugars concentrations in hydrolysates of sugar beet pulp and spent hops were by 88.9% and 59.4% higher compared to undigested materials. The highest yield of biogas was obtained from the enzymatic hydrolysate of sugar beet pulp (183.39 mL/d from 1g COD at fermenter loading with organic matter of 5.43 g COD/L × d). Fermentation of sugar beet pulp gave 19% less biogas. Methane fermentation of spent hops hydrolysate yielded 121.47 mL/d biogas from 1g COD (at 6.02 g COD/L × d, 13% more than from spent hops). These results provide evidence that suitable enzymatic pretreatment of lignocellulosic wastes improve biogas yield from anaerobic fermentation.     

Bioconversion of industrial wastes: paint sludge from automotive manufacturing

The compostability of water-based paint sludge originating from the automotive industry was investigated. Six reactors were operated. Wastewater treatment sludge from the same industry was used as additional substrate, and corncob was used as a bulking agent. The level of paint sludge within the compost mixtures varied between 55 and 85%. All reactors yielded a temperature increase up to thermophilic phase levels (>?40 °C) for a minimum of 5 days, and organic matter and C/N losses were observed. BTEX concentrations decreased during composting. Nickel and tin levels in the final product exceeded the legal compost limits. The calorific value of the compost mixtures increased from 9532 to 18774 kJ/kg at the end of the composting process. It was seen that the process applied in this study can be utilized as a biodrying step before the usage of paint sludge at cement kilns as additional fuel.     

Comparison of compostable bags and aerated bins with conventional storage systems to collect the organic fraction of municipal solid waste from homes. A Catalonia case study

The separation of biowaste at home is key to improving, facilitating and reducing the operational costs of the treatment of organic municipal waste. The conventional method of collecting such waste and separating it at home is usually done by using a sealed bin with a plastic bag. The use of modern compostable bags is starting to be implemented in some European countries. These compostable bags are made of biodegradable polymers, often from renewable sources. In addition to compostable bags, a new model of bin is also promoted that has a perforated surface that, together with the compostable bag, makes the so-called “aerated system”. In this study, different combinations of home collection systems have been systematically studied in the laboratory and at home. The results obtained quantitatively demonstrate that the aerated bin and compostable bag system combination is effective at improving the collection of biowaste without significant gaseous emissions and preparing the organic waste for further composting as concluded from the respiration indices. In terms of weight loss, temperature, gas emissions, respiration index and organic matter reduction, the best results were achieved with the aerated system. At the same time, a qualitative study of bin and bag combinations was carried in 100 homes in which more than 80% of the families participating preferred the aerated system.     

Processing of metallurgical residues by flotation - bench-scale studies on two industrial products

Resource recovery from two metallurgical residues by flotation was investigated applying an electrostatic model to select initial conditions. The first, a sulphation roast/water leach residue, was processed to float lead sulphate, comparing dodecylamine and xanthate collectors. From the second, a neutralization residue, gypsum, was recovered by reverse flotation of ferric hydroxide, comparing oleate and sulphonate collectors. In both cases, further upgrading by acid leaching was considered.     

Evolution of organic matter during composting of different organic wastes assessed by CPMAS 13C NMR spectroscopy

In this paper, the evolution of organic matter (OM) during composting of different mixtures of various organic wastes was assessed by means of chemical analyses and CPMAS ¹³C NMR spectroscopy measured during composting. The trends of temperatures and C/N ratios supported the correct evolution of the processes. The CPMAS ¹³C NMR spectra of all composting substrates indicated a reduction in carbohydrates and an increase in aromatic, phenolic, carboxylic and carbonylic C which suggested a preference by microorganisms for easily degradable C molecules. The presence of hardly degradable pine needles in one of the substrates accounted for the lowest increase in alkyl C and the lowest reduction in carbohydrates and carboxyl C as opposite to another substrate characterized by the presence of a highly degradable material such as spent yeast from beer production, which showed the highest increase of the alkyl C/O-alkyl C ratio. The highest increase of COOH deriving by the oxidative degradation of cellulose was shown by a substrate composed by about 50% of plant residues. The smallest increases in alkyl C/O-alkyl C ratio and in polysaccharides were associated to the degradation of proteins and lipids which are major components of sewage sludge. Results obtained were related to the different composition of fresh organic substrates and provided evidence of different OM evolution patterns as a function of the initial substrate composition.     

Semivolatile organic decay rates in pilot-scale solid- and slurry-phase bioreactors

A variety of process byproducts and residues were reclaimed at the Brio Refining Superfund site, an abandoned jet fuel refinery located near Houston, Texas. Among the operations that took place at the site were regeneration of acrylonitrile synthesis catalysts, styrene reprocessing still bottoms to recover ethylbenzene, and the attempted reclamation of 1,2-dichloroethane from vinyl chloride process residues. Incoming process byproducts and residues were stored in unlined impoundments before reclamation, until the Texas Air Control Board had the impoundments closed under court order in 1979. After the pits were closed, two pilot-scale bioremediation demonstrations were performed on the backfilled impoundments. The results of these studies indicated that bioremediation of the organic residues and affected soils at the site was included as an acceptable treatment technology in the Record of Decision. This article compares the degradation rates achieved by the two different biological treatment processes used to treat the organic material in the impoundments.     

Microbial Fe(III) Reduction in Acidic Mining Lake Sediments after Addition of an Organic Substrate and Lime

To elucidate the role of Fe(III) reduction in mining lake sediments amended with organic substrates, we performed a large (10 m diameter) enclosure experiment in which sediments were amended with Carbokalk, a waste product from sugar industry containing organic carbon and lime. Fe(III) reduction rates were determined monthly by measuring the accumulation of Fe(II) in the sediments in the field. Fe(III) reduction rates were also determined by incubating sediment samples with synthetic Fe(III) oxyhydroxide under in situ temperature in the laboratory. Sulfate reduction was selectively inhibited in the Fe(III) reduction experiments by addition of sodium molybdate. Sulfate reduction was measured by accumulation of reduced inorganic sulfides in the field and by ³⁵S radiotracer using a core injection technique. Sediment incubation and determination of sulfate reduction rates with radiotracer showed that sulfate reduction and direct microbial Fe(III) reduction occured simultaneously in the upper centimeters of the sediments and that both processes contributed to alkalinity generation. However, Fe(III) reduction was the initial process and rates were at least 3.5 fold higher than sulfate reduction rates. The results indicate that the presence of suitable anions for Fe(II) precipitation as carbonate or sulfide is needed in order to prevent loss of potential alkalinity by Fe(II) diffusion and reoxidation in the water column.