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 composts. In the aeration of raw sludge at 20 degrees C the DEHP removals were 33-41% and 50-62% in 7 and 28 days, respectively. Both composting and aeration are concluded to have the potential to reduce the DEHP contents typically found in sewage sludges to levels acceptable for agricultural use.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

Effects of long-term soil amendment with sewage sludges on soil humic acid thermal and molecular properties

Sewage sludges are frequently used as soil amendments due to their high contents of organic matter and nutrients, particularly N and P. However, their effects upon the chemistry of soil humic acids, one of the main components of the soil organic matter, need to be more deeply studied in order to understand the relation between organic matter structure and beneficial soil properties. Two sewage sludges subjected to different types of pre-treatment (composted and thermally dried) with very different chemical compositions were applied for three consecutive years to an agricultural soil under long-term field study. Thermal analysis (TG–DTG–DTA) and solid-state ¹³C NMR spectroscopy were used to compare molecular and structural properties of humic acids isolated from sewage sludges, and to determine changes in amended soils. Thermally dried sewage sludge humic acids showed an important presence of alkyl and O/N-alkyl compounds (70%) while composted sludge humic acids comprised 50% aromatic and carbonyl carbon. In spite of important differences in the initial chemical and thermal properties of the two types of sewage sludges, the chemical and thermal properties of the soil humic acids were quite similar to one another after 3 years of amendment. Long-term application of both sewage sludges resulted in 80–90% enrichment in alkyl carbon and organic nitrogen contents of the soil humic acid fraction.     

Binding of polycyclic aromatic hydrocarbons by humic acids formed during composting

Binding of two model polycyclic aromatic hydrocarbons (PAHs), phenanthrene and pyrene, by humic acids (HAs) isolated from an organic substrate at different stages of composting and a soil was investigated using a batch fluorescence quenching method and the modified Freundlich model. With respect to soil HA, the organic substrate HA fractions were characterized by larger binding affinities for both phenanthrene and pyrene. Further, isotherm deviation from linearity was larger for soil HA than for organic substrate HAs, indicating a larger heterogeneity of binding sites in the former. The composting process decreased the binding affinity and increased the heterogeneity of binding sites of HAs. The changes undergone by the HA fraction during composting may be expected to contribute to facilitate microbial accessibility to PAHs. The results obtained also suggest that bioremediation of PAH-contaminated soils with matured compost, rather than with fresh organic amendments, may result in faster and more effective cleanup.     

Principles of microbial PAH-degradation in soil

Interest in the biodegradation mechanisms and environmental fate of polycyclic aromatic hydrocarbons (PAHs) is motivated by their ubiquitous distribution, their low bioavailability and high persistence in soil, and their potentially deleterious effect on human health. Due to high hydrophobicity and solid-water distribution ratios, PAHs tend to interact with non-aqueous phases and soil organic matter and, as a consequence, become potentially unavailable for microbial degradation since bacteria are known to degrade chemicals only when they are dissolved in water. As the aqueous solubility of PAHs decreases almost logarithmically with increasing molecular mass, high-molecular weight PAHs ranging in size from five to seven rings are of special environmental concern. Whereas several reviews have focussed on metabolic and ecological aspects of PAH degradation, this review discusses the microbial PAH-degradation with special emphasis on both biological and physico-chemical factors influencing the biodegradation of poorly available PAHs.     

Decontamination of polycyclic aromatic hydrocarbons and nonylphenol from sewage sludge using hydroxypropyl-β-cyclodextrin and evaluation of the toxicity of leachates

A decontamination technique based in cyclodextrin extraction has been developed to eliminate nonylphenol (NP) and 16 polycyclic aromatic hydrocarbons (PAHs; the US Environmental Protection Agency priority pollutants list) from sewage sludge. In a first step, PAHs and NP were characterised in six sludges to determine contamination levels according to limit values proposed by the European Union Sludge Directive draft. There were few variations in the total PAHs content with levels of 1.88 to 3.05 mg kg^?1. Three-ring PAHs predominated, but fluoranthene and pyrene were also present. None of the sludge exceeded the PAHs limit proposed by the European Union’s draft Directive. On the contrary, NP content in four of the six sludges was over the recommended limits of 50 mg kg^-1 for NP ethoxylates. With the aim of obtaining NP values below the concentration limits proposed to use the sewage sludge as agricultural amendments, a preliminary study using hydroxypropyl-β-cyclodextrin (HPBCD) extractions as a decontamination technique was carried out. About 90 % of NP content was removed with only one extraction with HPBCD, whereas after three sequential extractions using an aqueous solution without HPBCD, the NP extraction percentage was less than 1 %. Simultaneously, PAHs extraction percentages obtained with HPBCD were also much higher than when aqueous solution was used, especially in the case of two- and three-ring PAHs. Finally, the potential environmental hazard of HPBCD leachates to aquatic organisms (Daphnia magna) was tested. These results indicate that the treatment of sewage sludge with cyclodextrin could allow their safe use as fertiliser in agriculture.     

Removal of PAHs from laboratory columns simulating the humus upper layer of vertical flow constructed wetlands

Removal of three polycyclic aromatic hydrocarbons or PAHs (fluoranthene, pyrene and benzo(k)fluoranthene) from two types of PAH-contaminated effluents was investigated using four laboratory columns filled with two different organic media: a green compost and a layer coming from the first stage of vertical flow constructed wetlands. Synthetic runoff polluted by polycyclic aromatic hydrocarbons were fed through the columns during a period of two months. After a period of hydrodynamic stabilisation, the results showed a great adsorption of PAHs (>95%) on the solid media due to their large adsorption capacities. Leaching of these compounds by water was monitored. The concentrations of PAHs in leaching samples indicated that PAHs were strongly adsorbed on organic substrates and that lixiviation was limited. Fluoranthene metabolites were also investigated. Accumulation of metabolites was transitory and located in the first few cm of the media, as was observed for PAH concentrations. A toxicity test of leachates based on the inhibition of the bioluminescence of luminescent bacteria Vibrio fischeri indicated a low inhibition which can be enhanced by metal traces.     

Monitoring polycyclic aromatic hydrocarbons (PAHs) and heavy metals in urban soil,compost and vegetation

Samples of urban surface soil, composts, leaves from avenue limetrees and grass from park areas of the city of Basel (Switzerland) were analysed for polycyclic aromatic hydrocarbons (PAHs) and heavy metals. Generally, significant lower levels of PAHs (10 times lower) and heavy metals (3–70 times lower) were found in vegetation samples than in composts or soils. The concentrations of PAHs in soil and compost samples were in the same order of magnitude although 10–100-times higher in comparison to data given for rural soils in other studies, whereas heavy metal contents in urban soils and composts were 2–3 times higher than in rural samples. Using multivariate statistical analysis, it was possible to define similarities or special characteristics of single substances or substance groups in a given matrix reflecting their chemical properties and providing information on their specific emission sources.     

Polycyclic aromatic hydrocarbons in fuel-oil contaminated soils, Antarctica

Where fuel oil spills have occurred on Antarctic soils polycyclic aromatic hydrocarbons (PAH) may accumulate. Surface and subsurface soil samples were collected from fuel spill sites up to 30 years old, and from nearby control sites, and analysed for the 16 PAHs on the USEPA priority pollutants list, as well as for two methyl substituted naphthalenes, 1-methylnaphthalene and 2-methylnaphthalene. PAH levels ranged from 41-8105 ng g-1 of dried soil in the samples from contaminated sites and were below detection limits in control site samples. PAH were detected in surface soils and had migrated to lower depths in the contaminated soil. The predominant PAH detected were naphthalene and its methyl derivatives.     

Effect of Sphingobium yanoikuyae B1 inoculation on bacterial community dynamics and polycyclic aromatic hydrocarbon degradation in aged and freshly PAH-contaminated soils

Sphingobium yanoikuyae B1 is able to degrade a range of polycyclic aromatic hydrocarbons (PAHs) and as a sphingomonad belongs to one of the dominant genera found in PAH-contaminated soils. We examined the ecological effect that soil inoculation with S. yanoikuyae B1 has on the native bacterial community in three different soils: aged PAH-contaminated soil from an industrial site, compost freshly contaminated with PAHs and un-contaminated compost. Survival of S. yanoikuyae B1 was dependent on the presence of PAHs, and the strain was unable to colonize un-contaminated compost. Inoculation with S. yanoikuyae B1 did not cause extensive changes in the native bacterial community of either soil, as assessed by denaturing gel electrophoresis, but its presence led to an increase in the population level of two other species in the aged contaminated soil community and appeared to have an antagonistic affect on several members of the contaminated compost community, indicating niche competition.     

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.     

Organic pollutant burden of the giant mussels Choromytilus chorus from the south-central Chilean coast

A comparative quantitative analysis was made on the contents of organochlorines (OCh) and polycyclic aromatic hydrocarbons (PAH) in tissues of the giant mussel Choromytilus chorus from three bays in south-central Chile exposed to various degrees of pollutant input. Mussels from the three bays contained levels of OCh near the detection limits of method, with a tendency to be slightly higher in the polluted bay (San Vicente) than in the other bays (Corral and Yaldad). PAH levels and types in Corral and Yaldad were well below of carcinogenicity permitted in mussels for human consumption.     

Heavy metal speciation and phytotoxic effects of three representative sewage sludges for agricultural uses

The environmental impact of sewage sludges depends on the availability and phytotoxicity of their heavy metal. The influence of representative sludges (dewatered anaerobic, pelletization, and composted sludge) on the availability of heavy metals, and their effects on seed germination were compared. The total heavy metal concentrations were below the maximum permitted for land-applied waste and the differences among them were small. The DTPA-extracted metal concentrations were rather different. The sequential extraction of the compost showed a slight increase in Cd and Cu availability, and a decrease in the availability of Fe, Mn, Ni and Zn. Pelletization increased the availability of Ni and slightly reduced that of Cr. The dewatering sludge led to greater availability of Cr and Mn but reduced the concentration of Cd. The three different sludges also affected seed germination and root elongation in different ways. The most serious adverse effects were caused by the dewatered sludge extract.     

A passive air sampler for characterizing the vertical concentration profile of gaseous phase polycyclic aromatic hydrocarbons in near soil surface air

Air-soil exchange is an important process governing the fate of polycyclic aromatic hydrocarbons (PAHs). A novel passive air sampler was designed and tested for measuring the vertical concentration profile of 4 low molecular weight PAHs in gaseous phase (PAH_LMW4) in near soil surface air. Air at various heights from 5 to 520 mm above the ground was sampled by polyurethane foam disks held in down-faced cartridges. The samplers were tested at three sites: A: an extremely contaminated site, B: a site near A, and C: a background site on a university campus. Vertical concentration gradients were revealed for PAH_LMW4 within a thin layer close to soil surface at the three sites. PAH concentrations either decreased (Site A) or increased (Sites B and C) with height, suggesting either deposition to or evaporation from soils. The sampler is a useful tool for investigating air-soil exchange of gaseous phase semi-volatile organic chemicals.     

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below the legal threshold. Overall, the Fl/Fl + Py diagnostic ratio revealed that PAHs had a petrogenic origin. VOC levels, except for two notable exceptions near Palermo landfill, were always below the legal limit. As concerns PCB levels, several samples were found positive with levels exceeding the legal limits. It is worth noting that the % PCB distribution differs from that of commercial compositions. In parallel, some samples of groundwater containing PCDDs and PCDFs exceeding the legal threshold were also found. Among the 17 congeners monitored, the most abundant were the highest molecular weight ones.

     

Detection of carcinogenic amino-alpha-carbolines and amino-gamma-carbolines in diesel-exhaust particles

Diesel-exhaust particles are known to contain mutagenic and carcinogenic chemicals. The aim of this study was to determine whether carcinogenic amino-alpha-carbolines and amino-gamma-carbolines are present in diesel-exhaust particles. These carcinogens which were originally isolated from pyrolysates of proteins and amino acids have been detected in diesel-exhaust particles obtained from two test vehicles as well as in standard materials of automobile-exhaust particles obtained from National Institute for Environmental studies. The levels of these carcinogens were far less than those of polycyclic aromatic hydrocarbons such as benzo[a]pyrene. However, the presence of these amino-alpha-carbolines and amino-gamma-carbolines in diesel-exhaust particles suggests that these compounds are environmental pollutants and also that diesel-exhaust is one of the sources of these carcinogens in the outdoor environment.     

Effects of heterocyclic PAHs (N, S, O) on the biodegradation of typical tar oil PAHs in a soil/compost mixture

The interaction phenomena during the biodegradation of typical coal tar polycyclic aromatic hydrocarbons and their heterocyclic analogues (N, S, O) were investigated in an artificially contaminated AhA1-horizon/compost mixture. All compounds were partly or completely biodegraded. Degradation of two- to five-ring PAHs was inhibited by the presence of hetero-PAHs, whereas degradation of just some hetero-PAHs was inhibited by the presence of PAHs. Among the hetero-PAHs the sulphur-containing compounds were less susceptible to degradation than the corresponding oxygen- or nitrogen-containing analogues. The basic azaarene acridine showed an extreme persistence and strong sorption to the soil matrix proved by an increase of recovery after saponification of the soil matrix.     

典型禾本科植物对石油污染土壤的修复作用

石油类污染物对土壤生态系统的结构与功能造成了较为严重的破坏,影响植物的生长,甚至直接影响到人类健康。选择典型禾本科植物-高粱和玉米,通过盆栽实验,种植于模拟石油污染的土壤中,植物成熟收割后,通过测定土壤中总石油烃的含量,植物体中多环芳烃和直链烷烃的含量,研究高粱和玉米对石油污染土壤的修复作用。结果显示:在种植高粱、玉米后,土壤中总石油烃含量明显降低,并且在收获的高粱、玉米植物体中直链烷烃和多环芳烃含量明显高于空白对照组(未检出)。说明高粱、玉米对石油烃具有一定的去除作用,且高粱对土壤中石油烃的去除作用高于玉米;高粱、玉米对土壤中的多环芳烃和直链烷烃具有一定的积累与富集作用。     

Use of 15N-depleted artificial compost in bound residue studies

Association of bound residues to soil humic matter may be accomplished by different binding mechanisms such as sequestration in hydrophobic interiors of the organic material or covalent linkage to the organic matter. The structures and chemical environments of compounds can be observed by NMR spectroscopy. We applied 15N-NMR spectroscopy to study the soil-bound residues of 15N-labeled simazine. As the 15N-isotope has a low sensitivity and natural abundance 15N-NMR experiments require long measurement times and often result in low signal-to-noise (S/N) ratios. Therefore, in addition to the use of 15N-labeled simazine, 15N-depleted compost was used to reduce the amount of background signal and enhance the sensitivity. The compost was produced from maize and wheat plants grown on sand with 15N-depleted NH4NO3 as sole nitrogen source. The plants were freeze-dried, ground and mixed with sand for composting. After a composting period of 224 days analysis of the compost revealed a 15N-content of 267 ppm as opposed to a natural abundance of 3650 ppm. Characterization of this artificial compost produced parameter values similar to those of a natural compost. The 13C-NMR-spectra of the humic and fulvic acids during different stages of maturity showed that there was a shift from single-bond functional groups to more complex double-bond and aromatic structures. Experiments with this compost showed an increased signal intensity. The improved sensitivity made it possible to obtain interpretable NMR signals in contrast to experiments with 15N-simazine on native soil where no signals were detectable. The data indicated that the bound residues of simazine are composed of metabolites resulting from N-dealkylation and triazine ring destruction. Silylation of the bound residues showed a very strong binding of the residues to the matrix as only a small fraction could be solubilized.     

Integrated waste management in a zone of northern Italy: compost production and use, and analytical control of compost, soil, and crop

Agricultural soils of two Italian maize farms were treated for five years with an industrially produced high-quality compost. Cattle manure and the usual mineral fertilizer were used for comparison purposes. The effects of the organic and mineral fertilizer treatments were studied by analyzing the compost and manure, cultured soils, and harvested material. The grain yield was also determined. Organic fertilization improved soil pH, CEC, content of organic matter and NPK. Soil respiration and N mineralization were found to be higher than in the purely mineral-treated soil. Plant K take-up was improved, whereas grain yield was not affected. It was confirmed that organic fertilization, particularly compost use, maintained and increased soil fertility. The study demonstrated the feasibility of using in loco analytical facilities to follow the entire recycling process-from waste to compost production-and the use of the final product in the field.