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. Without ISM the contribution of aromatic structures to the total pyrogram was considerably greater than that of the aliphatics. Increase of the pyrolysis temperature from 450 degrees C to 600 degrees C had smaller effect on the proportions and composition of the compounds studied than increase from 350 degrees C to 450 degrees C.     

Charge characteristics of humic and fulvic acids: comparative analysis by colloid titration and potentiometric titration with continuous pK-distribution function model

Charge characteristics of humic and fulvic acids of a different origin (inshore soils, peat, marine sediments, and soil (lysimetric) waters) were evaluated by means of two alternative methods - colloid titration and potentiometric titration. In order to elucidate possible limitations of the colloid titration as an express method of analysis of low content of humic substances we monitored changes in acid-base properties and charge densities of humic substances with soil depth, fractionation, and origin. We have shown that both factors - strength of acidic groups and molecular weight distribution in humic and fulvic acids - can affect the reliability of colloid titration. Due to deviations from 1:1 stoichiometry in interactions of humic substances with polymeric cationic titrant, the colloid titration can underestimate total acidity (charge density) of humic substances with domination of weak acidic functional groups (pK>6) and high content of the fractions with molecular weight below 1kDa.     

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.     

Copper(II) complexation by humic and fulvic acids from pig slurry and amended and non-amended soils

The effect of the consecutive annual additions of pig slurry at rates of 0 (control), 90 and 150 m3 ha(-1) y(-1) over a 4-year period on the binding affinity for Cu(II) of soil humic acids (HAs) and fulvic acids (FAs) was investigated in a field plot experiment under semiarid conditions. A ligand potentiometric titration method and a single site model were used for determining the Cu(II) complexing capacities and the stability constants of Cu(II) complexes of HAs and FAs isolated from pig slurry and control and amended soils. The HAs complexing capacities and stability constants were larger than those of the corresponding FA fractions. With respect to the control soil HA, pig-slurry HA was characterized by a much smaller binding capacity and stability constant. Amendment with pig slurry decreased the binding affinity of soil HAs. Similar to the corresponding HAs, the binding affinity of pig-slurry FA was much smaller while that of amended-soil FAs were slightly smaller when compared to the control soil FA. The latter effect was, however, more evident with increasing the amount of pig slurry applied to soil per year and the number of years of pig slurry application.     

Potential availability of heavy metals to phytoextraction from contaminated soils induced by exogenous humic substances

Effective phytoremediation of soils contaminated by heavy metals depends on their availability to plant uptake that, in turn, may be influenced by either the existing soil humus or an exogenous humic matter. We amended an organic and a mineral soil with an exogenous humic acid (HA) in order to enhance the soil organic carbon (SOC) content by 1% and 2%. The treated soils were further enriched with heavy metals (Cu, Pb, Cd, Zn, Ni) to a concentration of 0, 10, 20, and 40 microg/g for each metal and allowed to age at room temperature for 1 and 2 months. After each period, they were extracted for readily soluble and exchangeable (2.5% acetic acid), plant-available (DTPA, Diethylentriaminepentaacetic acid), and occluded (1 N HNO(3)) metal species. Addition of HA generally reduced the extractability of the soluble and exchangeable forms of metals. This effect was directly related to the amount of added HA and increased with ageing time. Conversely, the potentially plant-available metals extracted with DTPA were generally larger with increasing additions of exogenous HA solutions. This was attributed to the formation of metal-humic complexes, which ensured a temporary bioavailability of metals and prevented their rapid transformation into insoluble species. Extractions with 1 N HNO(3) further indicated that the added metals were present in complexes with HA. The observed effects appeared to also depend on the amount of native SOC and its structural changes with ageing. The results suggest that soil amendments with exogenous humic matter may accelerate the phytoremediation of heavy metals from contaminated soil, while concomitantly prevent their environmental mobility.     

Phytoextraction of cadmium and zinc from arable soils amended with sewage sludge using Thlaspi caerulescens: development of a predictive model

The objectives of this study were to assess the potential for using Thlaspi caerulescens as a phytoextraction plant and develop a user-advice model, which can predict the frequency of phytoextraction operation required under prescribed conditions. Pot and field trials were conducted using soil collected from a dedicated sewage sludge disposal facility. Soil amendments (sulphuric acid, potassium chloride and EDTA) intended to increase Cd solubility were also tested. Predictive models of Cd and Zn uptake were developed which were able to reproduce the observed pH-dependence of Cd uptake with an apparent maximum around pH 6. Chemical treatments did not significantly increase the uptake of Cd. The periodic use of phytoextraction with T. caerulescens to maintain soils below statutory metal concentration limits, when modern sewage sludges are repeatedly applied, seems very attractive given the non-intrusive and cost-effective nature of the process. The major limitations lie with the large-scale husbandry of T. caerulescens.     

Behaviour of oxyfluorfen in soils amended with edaphic biostimulants/biofertilizers obtained from sewage sludge and chicken feathers. Effects on soil biological properties

We studied the behaviour of oxyfluorfen herbicide at a rate of 4 l ha^?1 on biological properties of a Calcaric Regosol amended with two edaphic biostimulants/biofertilizers (SS, derived from sewage sludge; and CF, derived from chicken feathers). Oxyfluorfen was surface broadcast on 11 March 2013. Two days after application of oxyfluorfen to soil, both biostimulants/biofertilizers (BS) were also applied to the soil. An unamended soil without oxyfluorfen was used as control. For 2, 4, 7, 9, 20, 30, 60, 90 and 120 days of the application of herbicide to the soil and for each treatment, the soil dehydrogenase, urease, β-glucosidase and phosphatase activities were measured. For 2, 7, 30 and 120 days of the application of herbicide to the soil and for each treatment, soil microbial community was determined. The application of both BS to soil without the herbicide increased the enzymatic activities and soil biodiversity, mainly at 7 days of beginning the experiment. However, this stimulation was higher in the soil amended with SS than for CF. The application of herbicide in organic-amended soils decreased the inhibition of soil enzymatic activities and soil biodiversity. Possibly, the low-molecular-weight protein content easily assimilated by soil microorganisms is responsible for less inhibition of these soil biological properties.     

钢丝绳行业污泥特性及挥发回转窑处理技术研究

富含重金属污泥的处置和回收利用至今常有技术上的难点,更难以实现工业化的回收利用。分析研究了南通地区钢丝绳生产废水处理过程中所产生污泥的组分和特性,并与常见几类污泥作了比较。结果表明,具有高灰分和低热值的这种污泥的燃烧特性和电镀污泥相似,其主要组分Pb、Zn和Fe的含量分别为0.42％～0.58％、1.11％～5.33％...     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Acid-base properties of water-soluble organic matter of forest soils, studied by the pK-spectroscopy method

Using the potentiometric titration and pK spectroscopy method, acid-base properties of water-soluble organic matter of forest soils have been studied. Five acidic classes composed of different substances with pK(a) values around 3.6; 4.8; 6.7; 8.7 and 9.7 have been identified. Testing the properties of soluble soil fraction, it is to be taken into account that when it is isolated from non-soluble soil matter, some water-soluble substances remain in soil and do not pass into the solution. Most firmly adsorbed in soil are water-soluble components with pK(a) 9.6-9.8.     

Detection of copper(II) and zinc(II) binding to humic acids from pig slurry and amended soils by fluorescence spectroscopy

The effect of the consecutive annual additions of pig slurry at rates of 0 (control), 90 and 150 m3 ha(-1) yr(-1) after a 7-year period on the Cu(II) and Zn(II) binding behavior of soil HAs was investigated in a field experiment. A fluorescence titration method and a single site model were used for determining metal ion complexing capacities and stability constants of metal ion complexes of HAs isolated from pig slurry and unamended and amended soils. With respect to control soil HA, pig-slurry HA featured much smaller Cu(II) and Zn(II) binding capacities and stability constants. Pig-slurry application to soil decreased Cu(II) and Zn(II) complexing capacities and binding affinities of soil HA. These effects increased with increasing the rate per year of PS application to soil, and are expected to have a large impact on bioavailability, mobilization, and transport of Cu(II) and Zn(II) ions in pig slurry-amended soils.     

垃圾焚烧发电厂渗滤液MBR-NF截留液中腐植酸的超滤分离回收

垃圾焚烧发电厂渗滤液MBR-NF膜截留液因含有高浓度的难降解有机物和无机盐而难以处理。考虑其所含有机物大部分为腐植酸,可加于资源利用。本研究采用超滤对MBR-NF膜截留液中的腐植酸进行分离回收。实验结果表明,超滤能有效分离截留液中有机物和无机盐离子,分离因子与体积浓缩倍数(CF)呈良好的线性关系;回收样品的腐植酸含量达到36 g/L以上,重金属含量低于相关标准限值,表明采用超滤分离回收垃圾焚烧发电厂渗滤液MBR-NF截留液中的腐植酸是可行的。     

垃圾焚烧发电厂渗滤液MBR-NF截留液中腐植酸的超滤分离回收

垃圾焚烧发电厂渗滤液MBR-NF膜截留液因含有高浓度的难降解有机物和无机盐而难以处理。考虑其所含有机物大部分为腐植酸,可加于资源利用。本研究采用超滤对MBR—NF膜截留液中的腐植酸进行分离回收。实验结果表明,超滤能有效分离截留液中有机物和无机盐离子,分离因子与体积浓缩倍数（CF）呈良好的线性关系;回收样品的腐植酸含量达到36g／L以上,重金属含量低于相关标准限值,表明采用超滤分离回收垃圾焚烧发电厂渗滤液MBR-NF截留液中的腐植酸是可行的。     

The effect of heavy metals on dinitrogen fixation by Rhizobium-white clover in a range of long-term sewage sludge amended and metal-contaminated soils

An investigation was conducted to determine whether effective strains of Rhizobium leguminosarum biovar. trifolii capable of symbiotic N2 fixation with white clover (Trifolium repens) were present in a range of metal-contaminated soils. A number of historically sewage-amended sites (including experimental, pasture grassland and arable sites) were selected and compared with highly contaminated samples from abandoned heavy metal mines. Many sites had metal concentrations above the limits established by the UK Government, based on those developed by the European Commission (EC) for sludge-amended soils. Acetylene reduction activity (ARA) was used to screen the samples for effective N2 fixation. When the host plant was indigenous to the sward, rhizobia were found in the nodules and in the soil rhizosphere at all the sites tested. They were shown to be capable of effective symbiosis and N2 fixation, even though metal concentrations greatly exceeded the soil metal limits in some cases. However, nodulation failed to occur in some cases where T. repens was not indigenous to metal-contaminated soils. This indicated either that an ineffective rhizobial population was present, or that effective cells were absent from the soil. The influence of individual metals on ARA could not be determined conclusively because of the confounding effects of soil physicochemical variability and the presence of different metals at high concentrations together in the soil. However, Cd concentrations appeared to be particularly important in determining the presence of effective ARA in soils with no indigenous clover. In contrast to previous studies, the results presented here suggest that heavy metals may have had a quantitative effect on the free-living population of rhizobia, rather than a genetic effect.     

Microbial utilization and transformation of humic acid-like substances extracted from a mixture of municipal refuse and sewage sludge disposed of in a landfill

The purpose of the research was to establish whether humic acid-like substances (HA) related to municipal refuse disposed of in a landfill can resist microbial degradation and if they contribute, in that way, to long-term stabilization of landfill refuse. Using a mixture of 0.1 M Na(4)P(2)O(7) + 0.1 M NaOH, we extracted HA from municipal refuse mixed with sewage sludge and disposed of for up to 12 months, in a 40-m(3) model landfill. In laboratory experiments under aerobic conditions, up to 50% of HA was utilized as a supplementary source of nutrients by an assemblage of soil microorganisms in only 21 days. The microbial utilization was enhanced to over 80%, and up to 98%, respectively, if HA served as the sole source of carbon or nitrogen. Remaining HA which could be re-isolated from microbial cultures were lower in carbon (<12%) and nitrogen (<2.3%). Spectroscopic analysis (UV, Vis, FTIR) indicated losses, especially in aliphatic structural units, and a relative enhancement in aromatic structures. It was postulated that for their high degree of degradability, HA indigenous to that anthropogenic environment would not play an important role in the long-term stabilization of landfill refuse.     

Spectroscopic and molecular characterization of humic substances (HS) from soils and sediments in a watershed: comparative study of HS chemical fractions and the origins

Environmental Science and Pollution Research - Optical properties and molecular composition of humic substances (HS) can provide valuable information on the sources and the history of the...     

Environmental signals: synthetic humic substances act as xeno-estrogen and affect the thyroid system of Xenopus laevis

According to outdated paradigms humic substances (HS) are considered to be refractory or inert that do not directly interact with aquatic organisms. However, they are taken up and induce biotransformation activities and may act as hormone-like substances. In the present study, we tested whether HS can interfere with endocrine regulation in the amphibian Xenopus laevis. In order to exclude contamination with phyto-hormones, which may occur in environmental isolates, the artificial HS1500 was applied. The in vivo results showed that HS1500 causes significant estrogenic effects on X. laevis during its larval development and results of semi-quantitative RT-PCR revealed a marked increase of the estrogenic biomarker estrogen receptor mRNA (ER-mRNA). Furthermore, preliminary RT-PCR results showed that the thyroid-stimulating hormone (TSHbeta-mRNA) is enhanced after exposure to HS1500, indicating a weak adverse effect on T3/T4 availability. Hence, HS may have estrogenic and anti-thyroidal effects on aquatic animals, and therefore may influence the structure of aquatic communities and they may be considered environmental signaling chemicals.