0000000000138972
AUTHOR
Kari Hänninen
Historical and current progress in understanding the origin and structure of humic substances
Research into humic substances (HS) has focused selectively on the search for aromatic structures. All aromatic compounds are regarded as eligible HS constituents, whereas aliphatic, polysaccharide structural constituents are considered non-HS. Wet chemical methods for analysing HS produce 2–5% aromatic compounds from the original starting material. Only those compounds in the hydrophobic extraction phases are studied carefully. Compounds in the hydrophilic extraction phases, containing mainly aliphatics, are discarded. Solid-state NMR spectra from HS show 30–40% of carbon–carbon unsaturation, which is selectively interpreted as ‘aromatic’. No recognition is given to the fact that NMR spect…
A method for measuring low-weight carboxylic acids from biosolid compost
Concentration of low-weight carboxylic acids (LWCA) is one of the important parameters that should be taken into consideration when compost is applied as soil improver for plant cultivation, because high amounts of LWCA can be toxic to plants. The present work describes a method for analysis of LWCA in compost as a useful tool for monitoring compost quality and safety. The method was tested on compost samples of two different ages: 3 (immature) and 6 (mature) months old. Acids from compost samples were extracted at high pH, filtered, and freeze-dried. The dried sodium salts were derivatized with a sulfuric acid–methanol mixture and concentrations of 11 low-weight fatty acids (C1–C10) were a…
Occupational hygiene in a waste incineration plant
Abstract The Turku incineration plant was renovated in 1995 to meet the emission requirements of modern waste combustion facilities. It treats presorted municipal waste from 170,000 residents in the Turku area. In the plant, the incineration process produces several types of by-products having importance in terms of occupational hygiene. Although not obligated by the law, the management of the plant has a keen interest in occupational hygiene at the plant, which was studied from 1998 to 2001. Concentrations of microbes, endotoxins, and dust and the noise level were investigated in three different working areas. Microbe measurements were conducted with a six-stage impactor and using the CAMN…
Pyrolysis of humic acids from digested and composted sewage sludge
Humic acids (HAs) were extracted from four digested sewage sludge samples composted for four months, one, two and four years. HAs were pyrolyzed at three different temperatures applying both conventional and in situ methylation (ISM) pyrolysis. The pyrolysates were analyzed using gas chromatography-mass spectrometry (GC/MS). Derivatization (ISM) and pyrolysis temperature had dramatic effects on the composition and relative amounts of the pyrolysates. Among the derivatized HA fragments aliphatic compounds prevailed under all the pyrolysis conditions tested. Aromatic substances consisting mainly of guaiacyl-type compounds were detected in higher abundances only at elevated temperatures. Witho…
Ash in composting of source-separated catering waste.
Our earlier experiments in small composters (220 l) indicated the favourable effect of ash from co-incineration of sorted dry waste on the composting of catering waste. The aim of this new study was to clarify further, at a scale of 10 m3, the feasibility of using similar ash as an additive in composting.Source-separated catering waste was mixed with bulking agent (peat and wood chips) and fuel ash from a small (4 MW) district heating power plant. Three compost mixes (CM) were obtained: CM I with 0%, CM II with 10% and CM III with 20 wt.% of fuel ash. These three different mixes were composted in a 10-m3 drum composter as three parallel experiments for 2 weeks each, from January to April 20…
Biodeterioration of cardboard-based liquid containers collected for fibre reuse.
Liquid packaging board (LPB) collected in Germany is processed in Finland as recycled fibre and as plastic reject for incineration. The chemical, biological and physical changes occurring in recycled LPB bales were monitored during storage of six and 18 months. The moisture content in the core of the bales ranged from 7% to 53%, and pH values varied from 6.0 to 8.5. The average amount of mesophilic bacteria per container was 1.5 x 10(7) - 5 x 10(8), which means that recycled LPB pulp cannot be recommended for sanitary use. The concentration of CO2 inside the bale is an indicator of the activity of aerobic microorganisms and might be suitable for identifying deteriorated bales and removing t…
Occupational hygiene in biowaste composting
Source-separated biowastes from the Helsinki Metropolitan Area have been composted in open air windrows at Ammas suo, the Helsinki regional landfill in Espoo (Finland). The most significant problem encountered in the early stages of the process has been the formation of rancid odor causing human discomfort. The offensive odor was mainly due to car boxylic acids. A total of 110 organic compounds were detected in volatile emissions from windrow composts with an integrated sensory and instrumental method. Occasionally the temperatures in the windrows exceeded 80°C. Bacterial measurements also revealed substantial populations of bacte ria at 75°C. The concentrations of airborne microbes and en…
Carbohydrates as Chemical Constituents of Biowaste Composts and their Humic and Fulvic Acids
The decomposition of organic matter of source-separated biowaste during composting was followed during 18 months. Compost samples were fractionated into three parts: (i) hot water soluble extract (HWE) (ii) bitumen fraction and (iii) humic substances (humic acids (HA) and fulvic acids (FA)). Original compost samples and the HA and FA fractions were hydrolyzed with sulfuric acid for hexoses and pentoses. Quantitative spectrophotometric and qualitative GC/MS analyses of monosaccharides as trimethylsilyl ethers of the corresponding alditols were carried out.During composting, the amount of HA in the organic matter of the compost increased, the amounts of HWE and bitumen decreased and the amoun…
Occupational hygiene in a Finnish drum composting plant
Bioaerosols (microbes, dust and endotoxins) and volatile organic compounds (VOCs) were determined in the working air of a drum composting plant treating source-separated catering waste. Different composting activities at the Oulu drum composting plant take place in their own units separated by modular design and constructions. Important implication of this is that the control room is a relatively clean working environment and the risk of exposure to harmful factors is low. However, the number of viable airborne microbes was high both in the biowaste receiving hall and in the drum composting hall. The concentration (geometric average) of total microbes was 21.8 million pcs/m3 in the biowaste…
The Role of Excited Oxygen Molecules in the Formation of the Secondary Ozone Layer at 87 to 97 km
The secondary ozone layer is located at elevations of 87 to 97 km in the upper mesosphere – lower thermosphere. It overlaps with the ionospheric D-layer. Daytime intensive UV radiation is dissociating O2 molecules to O atoms and photoexcitating O2 molecules up to 11.07eV level. Ozone photolysis between the wavelengths of 118.7–121.6 nm produces three oxygen atoms from one ozone molecule. Collision reactions of O2(B3 Σu —) and O2(X3 Σg —, υ≥26) with O2(X3 Σg —, υ=0) produce additional oxygen atoms. The number of oxygen atoms is maintained at such a high level that a small but significant ozone concentration survives. UV radiation weakens radically during the night. The number of O atoms show…
Phytotoxicity of low-weight carboxylic acids.
Abstract Presence of low-weight carboxylic acids (LWCAs) can be the reason for phytotoxicity of green manures, treated bio-waste or digestates from biogas production applied to soils. As the phytotoxic concentrations of LWCA are poorly known, this work presents data on six acids (C 1 C 6 : formic, acetic, propionic, butyric, valeric, and caproic). Phytotoxicity was measured in acute (72 or 120 h) and subchronic (21 d) assays for seed germination, seedling elongation, and plant growth for garden cress Lepidium sativum and ryegrass Lolium multiflorum . The dose–response relationship was modeled using Weibull model. Results showed a trend that toxicity of LWCA increases with the length of the …
Contribution of Excited Ozone and Oxygen Molecules to the Formation of the Stratospheric Ozone Layer
The absorption of UV, visible and near IR radiation by O3 produces transient, electronically excited O3. The absorption of thermal IR radiation ( = 9.065, 9.596 and 14.267 µm) produces vibrationally excited O3 molecules. Thermal absorption is likely the main factor in the self-decay of O3. Photoexcitation of ground state by IR and red light radiation produces singlet oxygens and . Chemical reactions in the stratosphere produce them as well. When reacting with ozone, singlet oxygen produces O (3P) and . By doing so, they tend to maintain the prevailing ozone concentration and are thereby important for the stability of the ozone layer. During the daytime, O(1D), and reach their maximum concen…
Concentrations of monosaccharides in humic substances in the early stages of humification.
Deteriorated liquid packaging board (LPB) and biowaste compost are matrices, mainly consisting of cellulose, in the early stages of humification. Degradative studies on these matrices allow an examination of the role of carbohydrates in the synthesis of humic substances. Samples of different age were collected and divided by extraction into hot water extract (HWE), bitumen, humic acid (HA), fulvic acid (FA) and humin or residual fibre fractions. The following monosaccharides were identified in these fractions: L-arabinose, D-ribose, D-xylose, L-fucose, D-mannose, D-fructose, D-galactose, D-glucose, L-rhamnose and xylitol. The main component in all fractions was glucose. The concentrations o…
Effect of commercial mineral-based additives on composting and compost quality.
Abstract The effectiveness of two commercial additives meant to improve the composting process was studied in a laboratory-scale experiment. Improver A (sulphates and oxides of iron, magnesium, manganese, and zinc mixed with clay) and B (mixture of calcium hydroxide, peroxide, and oxide) were added to source-separated biowaste:peat mixture (1:1, v/v) in proportions recommended by the producers. The composting process ( T , emissions of CO 2 , NH 3 , and CH 4 ) and the quality of the compost (pH, conductivity, C/N ratio, water-soluble NH 4 –N and NO 3 –N, water- and NaOH-soluble low-weight carboxylic acids, nutrients, heavy metals and phytotoxicity to Lepidium sarivum ) were monitored during…
Low-weight carboxylic acids as potential risk factor of compost phytotoxicity
Being intermediates of organic matter degradation, low-weight carboxylic acids (LWCA) can occur at phytotoxic concentrations on bioactive soils or in the processed organic material applied to soil. While toxicity potentials and mixture effects of LWCA are still poorly known, the potential phytotoxicity of the biomaterials is difficult to assess. In the study effective concentrations (EC) of formic, acetic and propionic acids at non adjusted pH were obtained in short-term germination assays (48 h for cress, Lepidium sativum, and 120 h for ryegrass Lolium multiflorum) and subchronic growth assays (21d). Based on the EC values, LWCA inhibited more strongly plant growth than seed germination. I…
Removal of DEHP in composting and aeration of sewage sludge.
The potential of composting and aeration to remove bis(2-ethylhexyl) phthalate (DEHP) from municipal sewage sludge was studied with two dewatered sludges: raw sludge and anaerobically digested sludge. Composting removed 58% of the DEHP content of the raw sludge and 34% of that of the anaerobically digested sludge during 85 days stabilisation in compost bins. A similar removal for the anaerobically digested sludge was achieved in a rotary drum in 28 days. Less than 1% of DEHP was removed with the compost leachate. Although DEHP removal was greater from raw sludge compost than anaerobically digested sludge compost, the total and volatile solids removals were on the same level in the two compo…
Composting of bio-waste, aerobic and anaerobic sludges – Effect of feedstock on the process and quality of compost
In-vessel composting of three stocks with originally different degree of organic matter degradation was conducted for: (1) kitchen source-separated bio-waste (BW), (2) aerobic (AS) as well as (3) anaerobic sludges (AnS) from municipal wastewater treatment plant. Composting experiment lasted over a year. The highest activity of the process was in the BW compost. It was implied by the highest temperature, CO(2) release, ammonification and nitrification, intensive accumulation and removal of low-weight carboxylic acids (water- and NaOH-extractable). Between the sludges higher mineralization and CO2 release was in AnS, while ammonification and nitrification were higher in AS compost; no signifi…
Windrow composting of source separated kitchen biowastes in Finland
All households in the City of Jyväskylä have been required to source-separate their wastes since June 1996. The accumulation of kitchen biowaste was about 60 kg per resident in 1997, with an efficiency of more than 75%. The residents of almost 50% of the detached houses in the city opted for small-scale composting. Ensuing kitchen biowaste was surprisingly pure: the estimated content of non-compostable material was less than 0.1 % by weight. The biowastes were composted at the Mustankorkea waste station in open windrows. Adequate aeration of the windrows was guaranteed when the initial height of the windrow was less than 1.5 m and the blending ratio for biowaste and bulking agent was one t…
Occupational hygiene in terms of volatile organic compounds (VOCs) and bioaerosols at two solid waste management plants in Finland
Abstract Factors affecting occupational hygiene were measured at the solid waste transferring plant at Hyvinkaa and at the optic separation plant in Hameenlinna. Measurements consisted of volatile organic compounds (VOCs) and bioaerosols including microbes, dust and endotoxins. The most abundant compounds in both of the plants were aliphatic and aromatic hydrocarbons, esters of carboxylic acids, ketones and terpenes. In terms of odour generation, the most important emissions were acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene due to their low threshold odour concentrations. At the optic waste separation plant, limonene occurred at the highest concentration of all sin…
Structurally bound lipids in peat humic acids
Humic acids from highly decomposed peat were subjected to oxidation with alkaline cupric oxide (CuO) at 170°C (single oxidation). Oxidation products were isolated as three fractions, oxidized humic acids, fulvic acids and lipophilic compounds. Isolated oxidized humic acids were subsequently re-oxidized (sequential oxidation) under the same conditions, and released lipophilic compounds were isolated. Lipids released during single and sequential oxidations were determined using capillary gas chromatography and mass spectrometry. Identified compounds accounted for 3.3 and 0.12 wt.% of humic acid content, respectively. Lipid profiles of lipophilic fractions released during single and sequential…
Chemical characterization of peat fulvic acid fractions
Abstract Milled peat fulvic acid (FA) preparation was fractionated by XAD-8 and conventional extraction methods. The fractions were further analyzed by IR and NMR and subjected to cupric oxide (CuO) oxidation. Carbohydrates of polydisperse FA were mostly not retained in the XAD-8 fractionation. The intensity of the signals due to double bonded carbons was much greater in the 13 C and proton NMR spectrum of the XAD-8 retained fraction than in the spectra of the XAD-8 non-retained or XAD-8 non-treated fractions. In CuO oxidation the main products of all FA fractions were 4-hydroxybenzaldehyde and 4-hydroxyacetophenone, both indicators of 4-hydroxyphenylpropane building blocks. Their concentra…
Mechanical–biological waste treatment and the associated occupational hygiene in Finland
A special feature of waste management in Finland has been the emphasis on the source separation of kitchen biowaste (catering waste); more than two-thirds of the Finnish population participates in this separation. Source-separated biowaste is usually treated by composting. The biowaste of about 5% of the population is handled by mechanical-biological treatment. A waste treatment plant at Mustasaari is the only plant in Finland using digestion for kitchen biowaste. For the protection of their employees, the plant owners commissioned a study on environmental factors and occupational hygiene in the plant area. During 1998-2000 the concentrations of dust, microbes and endotoxins and noise level…