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.     

Long-term effect of sewage sludge application on soil humic acids

Sewage sludges are used in agriculture because they act as a fertilizer. Long-term studies are needed to evaluate the effect of sewage sludge on soil properties by paying particular attention to the soil organic matter. Soil plots were amended for 10 years with 1Mg dry matter ha(-1)year(-1) of sewage sludge. Chemical parameters such as total organic carbon (TOC), N, C/N ratio and CEC were determined when this period ended. Moreover, TOC was fractionated into humified and non-humified fractions. Humic acids (HA) were isolated and studied by elemental analysis, DRIFT, (1)H NMR and CPMAS 13C NMR spectroscopies. At the end of the tests, compared to the control soil, the sludge-amended soil did not exhibit change in total organic C and related humified fractions. However, the HA composition of the soil treated with sludge had developed an HA composition closer to that of the HA-sludge as a result of the enrichment of recalcitrant fractions contained in the sludge.     

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.     

Remediation of metal contaminated soil with mineral-amended composts

This study examined the use of two composts derived from green waste and sewage sludge, amended with minerals (clinoptilolite or bentonite), for the remediation of metal-contaminated brownfield sites to transform them into greenspace. Soils contaminated with high or low levels of metals were mixed with the mineral-enhanced composts at different ratios and assessed by leaching tests, biomass production and metal accumulation of ryegrass (Lolium perenne L.). The results showed that the green waste compost reduced the leaching of Cd and Zn up to 48% whereas the composted sewage sludge doubled the leachate concentration of Zn. However, the same soil amended with composted sewage sludge showed an efficient reduction in plant concentrations of Cd, Cu, Pb or Zn by up to 80%. The results suggest that metal immobilisation and bioavailability are governed by the formation of complexes between the metals and organic matter. The amendment with minerals had only limited effects.     

Sequential extraction of heavy metals during composting of sewage sludge

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.     

Di-(2-ethylhexyl)phthalate in sewage sludge and post-treated sludge: quantitative determination by HRGC-MS and mass spectral characterization

DEHP was quantified into sewage sludge, thermally dried sludge and compost samples from different areas of Catalonia (North East Spain) using high-resolution gas chromatography (HRGC) coupled to a mass spectrometry (MS). The aim of the work was to determine the evolution of this ubiquitous environmental contaminant along some post-treatment sludge processes, such as composting and thermally drying. DEHP concentration detected in some sludges are above the maximum limit suggested by the EC (100 ppm d.m.) for agricultural use. However, the composting and thermally drying reduce the amount of DEHP in sewage sludge to acceptable level for safe land application. The study was completed with the characterization and long-term observation of DEHP in sewage sludge, composted sludge and thermally dried sludge mixed with two types of soils. In all cases, the percentage of DEHP degraded was higher than 50% after 9 months of incubation.     

Acid-base properties of humic substances from composted and thermally-dried sewage sludges and amended soils as determined by potentiometric titration and the NICA-Donnan model

The acid-base properties of humic acids (HAs) and fulvic acids (FAs) isolated from composted sewage sludge (CS), thermally-dried sewage sludge (TS), soils amended with either CS or TS at a rate of 80 t ha(-1)y(-1) for 3y and the corresponding unamended soil were investigated by use of potentiometric titrations. The non-ideal competitive adsorption (NICA)-Donnan model for a bimodal distribution of proton binding sites was fitted to titration data by use of a least-squares minimization method. The main fitting parameters of the NICA-Donnan model obtained for each HA and FA sample included site densities, median affinity constants and widths of affinity distributions for proton binding to low and high affinity sites, which were assumed to be, respectively, carboxylic- and phenolic-type groups. With respect to unamended soil HA and FA, the HAs and FAs from CS, and especially TS, were characterized by smaller acidic functional group contents, larger proton binding affinities of both carboxylic- and phenolic-type groups, and smaller heterogeneity of carboxylic and phenolic-type groups. Amendment with CS or TS led to a decrease of acidic functional group contents and a slight increase of proton binding affinities of carboxylic- and phenolic-type groups of soil HAs and FAs. These effects were more evident in the HA and FA fractions from CS-amended soil than in those from TS-amended soil.     

Leaching of heavy metals and alkylphenolic compounds from fresh and dried sewage sludge

Reusing sewage sludge as a soil fertiliser has become a common alternative to disposal. Although this practice has a few benefits, it may contribute to the medium- and long-term contamination of the trophic chain because sewage sludge may contain heavy metals and organic contaminants. As the leaching of contaminants may depend on the sludge pre-treatment, the leaching of heavy metals (Cu, Ni, Pb, Zn and Cr) and alkylphenolic compounds (APCs) (octylphenol (OP), nonylphenol (NP), nonylphenol-mono-ethoxylate (NP₁EO)) was investigated in five fresh and 40 °C dried sewage sludge samples from north-eastern Spain. FT-IR analyses and full-scan GC-MS chromatograms showed that sludge drying changed the nature of organic compounds leading to changes in their solubility. Moreover, sludge drying led to a higher relative contribution of dissolved organic carbon than the particulate organic carbon in the leachates. Leaching of Pb, Zn and Cr was below 5 % in both fresh and dried sludge samples, whereas Cu and Ni leached at rates up to 12 and 43 %, respectively, in some of the dried sludge samples. The leaching yields of OP, NP and NP₁EO ranged from 1.3 to 35 % for fresh samples, but they decreased from 0.8 to 3.4 % in dried samples. The decrease in the leachability of APCs observed in dried sludge samples might be attributed to the fact that these compounds are associated with particulate organic matter, with significantly lower concentration or even absent in dried sludge than in fresh sludge samples. Therefore, it is recommended to dry the sludge before its disposal.     

Effect of physical forms of soil organic matter on phenanthrene sorption

The sorption coefficient, K(OC), of phenanthrene (PHE) has been reported to vary with different types of organic matter, leading to uncertainties in predicting the environmental behavior of PHE. Among the studies that relate organic matter properties to their sorption characteristics, physical conformation of organic matter is often neglected. In this work, organic matter samples of different physical forms were examined for their sorption characteristics. Dissolved humic acids (DHA) showed significantly higher K(OC) than the corresponding solid humic acids (SHA) from which the DHAs were made. The K(OC) of DHAs was found to be related to polarity, whereas K(OC) of SHAs increased with aliphatic carbon content. Soil particles were treated with H(2)O(2) to remove organic matter, and humic acid was coated on H(2)O(2)-treated soil particles to make organo-mineral complexes at pH 4, 7 and 10. Although the nonlinear sorption was apparent for SHAs and H(2)O(2)-treated soil particles, the organo-mineral complexes formed using these two components at pH 4, 7 and 10 exhibited relatively linear sorption at organic carbon content, f(OC)>0.5%. These results indicate that organic matter of the same composition may have different sorption properties due to different physical forms (or conformations). Nonlinear sorption for the complexes formed at pH 4 with lower f(OC) (<0.5%) was also discussed.     

Formation of volatile iodinated alkanes in soil: results from laboratory studies

Volatile iodinated organic compounds play an important role in the tropospheric photochemical system, but the current knowledge of the known sources and sinks of these alkyl iodides is still incomplete. This paper describes a new source of alkyl iodides from the pedosphere. Different organic-rich soils and humic acid were investigated for their release of volatile organoiodides. Six volatile organoiodides, iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane and 2-iodobutane were identified and their release rates were determined. We assume an abiotic reaction mechanism induced by the oxidation of organic matter by iron(III). The influence of iron(III), iodide and pH on the formation of alkyl iodides was investigated. Additionally, different organic substances regarded as monomeric constituents of humus were examined for the production of alkyl iodides. Two possible reaction pathways for the chemical formation of alkyl iodides are discussed. As humic acids and iron(III) are widespread in the terrestrial environment, and the concentration of iodide in soil is strongly enriched (compared to seawater), this soil source of naturally occurring organoiodides is suggested to contribute significantly to the input of iodine into the troposphere.     

Influence of dissolved humic substances on the leaching of MCPA in a soil column experiment

The influence of dissolved humic substances on the transport of (4-chloro-2-methylphenoxy) acetic acid (MCPA) in a sandy soil with a low organic carbon content was studied in a column experiment. Soil columns were eluted with aqueous solutions containing different fractions of humic substances. More than 70% of the applied compound was found in the leachate in all sandy soil experiments, but distinct differences were obtained depending on the composition of the eluent. The addition of both humic and fulvic acids to the eluent affected the leaching behaviour of MCPA. While the presence of humic acids increased and accelerated the movement of MCPA in the investigated sandy soil, fulvic acids caused the opposite effect: increased retention was observed relative to the control. We concluded that a possible carrier transport or retention strongly depends on the composition of the dissolved organic matter. Thus, changes in the composition of dissolved organic matter may affect MCPA movement into deeper soil layers.     

Phytoavailability and fractions of iron and manganese in calcareous soil amended with composted urban wastes

Little is known about the effects of applying composted urban wastes on the phytoavailability and distribution of iron (Fe) and manganese (Mn) among chemical fractions in soil. In order to study this concern several experiments in pots containing calcareous soil were carried out. The received treatments by adding separately two rates (20 and 80 Mg ha-1) of municipal solid waste (MSW) compost and/or municipal solid waste and sewage sludge (MSW-SS) co-compost. The cropping sequence was a lettuce crop followed by a barley crop. It was observed that treatments amended with composted urban wastes tended to promote slight increases in lettuce yield compared to the control. The highest Fe levels in lettuce were found when higher rates of MSW-SS co-compost were applied; these values were significant compared to those obtained in the other treatments. In all cases, the application of organic materials increased the concentration and uptake of Mn in lettuce compared to the control; however, these increases were significant only when higher rates of MSW compost were applied. The organic amendments had beneficial delayed effects on barley yields, showing, in most cases, significant increases compared to the control. In this context, treatments with MSW compost were found to be more effective than the equivalent treatments amended with MSW-SS co-compost. Compared to the control, composted urban wastes increased Fe concentration in straw and rachis, and decreased Fe concentration in barley grain. Similarly, a decreased concentration of Mn in the dry matter of barley crop grown in soils treated with composted urban wastes was observed.     

Microbially mediated cadmium sorption/desorption processes in soil amended with sewage sludge

A multi-compartment system was used to study the importance of microorganisms for Cd desorption from soil amended with sewage sludge and simultaneous resorption of the mobilized metal by soil constituents. Using this system made it possible to study the participation of microorganisms (Arthrobacter, Trichoderma), montmorillonite, humic acids, and iron oxides in resorption of the released Cd. A filter-sterilized water extract of root-free soil of pH 6.7 (RF) or RF supplemented with glucose (RFG) were used to mobilize Cd from soil at 14 degrees C in 48 h. Cadmium found in those extracts after 48-h incubation was recognized as bioavailable. Changes in pH values and enrichment of soil extracts with organic acids and siderophores resulted from microbial growth. RFG with lower pH and a higher content of ligands mobilized, on average, 40% of Cd introduced with sewage sludge amended soil, whereas RF mobilized only 20% of it. Sequential extractions of Cd at time 0 and Cd remaining in soil showed that RFG had mobilized Cd mostly from the fraction bound with Fe and Mn oxides. Microbial biomass accounted for only up to 3.4% (w/w) of the soil constituents used in the experiments but resorbed 25% of mobilized Cd. The chemical composition of mobilizing soil extracts and the solid-to-mobilizing-extracts volume ratio had a significant effect on the amount of bioavailable Cd. The results of the study suggest that microbial metabolites were involved in Cd mobilization, while the biomass of microorganisms was involved in Cd resorption as a biosorbent.     

Cumulative and Residual Effects of Repeated Sewage Sludge Applications: Forage Productivity and Soil Quality Implications in South Florida,USA (9 pp)

Background, Aim and Scope The cow-calf (Bos taurus) industry in subtropical United States and other parts of the world depends almost totally on grazed pastures. Establishment of complete, uniform stand of bahiagrass (BG) in a short time period is important economically. Failure to obtain a good BG stand early means increased encroachment of weeds and the loss of not only the initial investment costs, but production and its cash value. Forage production often requires significant inputs of lime, N fertilizer, and less frequently of P and K fertilizers. Domestic sewage sludge or biosolids, composted urban plant debris, waste lime, phosphogypsum, and dredged materials are examples of materials that can be used for fertilizing and liming pastures. Perennial grass can be a good choice for repeated applications of sewage sludge. Although sewage sludge supply some essential plant nutrients and provide soil property-enhancing organic matter, land-application programs still generate some concerns because of possible health and environmental risks involved. The objectives of this study were to evaluate the cumulative and residual effects of repeated applications of sewage sludge on (i) bahiagrass (BG, Paspalum notatum Flügge) production over years with (1997–2000) and without (2001–2002) sewage sludge applications during a 5-yr period, and (ii) on nutrients status of soil that received annual application of sewage sludge from 1997 to 2000 compared with test values of soils in 2002 (with no sewage sludge application) in South Florida.Methods The field experiment was conducted at the University of Florida Agricultural Research and Education Center, Ona, FL (27o26’N, 82o55’W) on a Pomona fine sandy soil. With the exception of the control, BG plots received annual sewage sludge and chemical fertilizers applications to supply 90 or 180 kg total N ha–1 yr–1 from 1997 to 2000. Land application of sewage sludge and fertilizer ceased in 2001 season. In early April 1998, 1999, and 2000, plots were mowed to 5-cm stubble and treated with the respective N source amendments. The experimental design was three randomized complete blocks with nine N-source treatments: ammonium nitrate (AMN), slurry biosolids of pH 7 (SBS7), slurry biosolids of pH 11 (SBS11), lime-stabilized cake biosolids (CBS), each applied to supply 90 or 180 kg N ha–1, and a nonfertilized control (Control). Application rates of sewage sludge were calculated based on the concentration of total solids in materials as determined by the American Public Health Association SM 2540G method and N in solids. The actual amount of sewage sludge applications was based on the amount required to supply 90 and 180 kg N ha–1. Sewage sludge materials were weighed in buckets and uniformly applied to respective BG plots. Soil samples were collected in June 1997, June 1999, and in June 2002 from 27 treatment plots. In 1997 and 1999, soil samples were collected using a steel bucket type auger from the 0- to 20-, 20- to 40-, 40- to 60-, and 60- to 100-cm soil depths. Forage was harvested on 139, 203, 257, and 307 day of year (DOY) in 1998; 125, 202, 257, and 286 DOY in 1999; 179, 209, 270, and 301 DOY in 2000; and on 156 and 230 DOY in 2002 (no sewage sludge applications) to determine the residual effect of applied sewage sludge following repeated application. Forage yield and soils data were analyzed using analysis of variance (PROC ANOVA) procedures with year and treatment as the main plot and sub-plot, respectively. As a result of significant year effects on forage yield, data were reanalyzed annually (i.e., 1998, 1999, 2000, and 2002).Results and Discussion All sewage sludges used in this study were of class B in terms of USEPA’s pathogens and pollutant concentration limit. Pathogen and chemical composition of the class B sewage sludge that were used in the study were all in compliance with the USEPA guidelines. The liquid sludge (SBS11) had the lowest fecal coliform counts (0.2 x 106 CFU kg–1) while the cake sewage sludge (CBS) had the greatest coliform counts of 178 x 106 CFU kg–1. The fecal coliform counts for SBS7 was about 33 x 106 CFU kg–1. Average soil test values in June 2002 exhibited: i) decrease in TIN (NO3-N + NH4-N), TP, K, Ca, Mg, Mn, and Fe; and ii) slight increase in Zn and Cu when compared with the June 1997 soil test results. The overall decrease in soil test values in 2002 might be associated with nutrient cycling and plant consumption. Although the average BG forage yield in 2002 (2.3 ± 0.7 Mg ha–1) was slightly lower than in 2000 (3.5 ± 1.2 Mg ha–1), yield differences in 2002 between the control (1.2 + 0.2 Mg ha–1) and treated plots (2.3 ± 0.5 Mg ha–1 to 3.3 ± 0.6 Mg ha–1) were indicative of a positive residual effect of applied sewage sludge. This study has shown that excessive build up of plant nutrients may not occur in beef cattle pastures that repeatedly received sewage sludge while favoring long-term increased forage yield of BG. All sources of N (sewage sludge and AMN) gave better forage production than the unfertilized control during years with sewage sludge application (1997–2000) and also during years with no sewage sludge application (2001–2002). The favorable residual effects of applied sewage sludge in 2002 may have had received additional boost from the amount of rainfall in the area.Conclusions Repeated applications of sewage sludge indicate no harmful effects on soil quality and forage quality. Our results support our hypothesis that repeated land application of sewage sludge to supply 90 and 180 kg N ha–1 would not increase soil sorption for nutrients and trace metals. Results have indicated that the concentrations of soil TIN and TP declined by almost 50% in plots with different nitrogen sources from June 1997 to June 2002 suggesting that enrichment of nitrogen and phosphorus is insignificant. The concentrations of soil nitrogen and phosphorus in 2002 following repeated application of sewage sludge were far below the contamination risk in the environment. The residual effect of these sewage sludge over the long term can be especially significant in many areas of Florida where only 50% of the 1 million ha of BG pastures are given inorganic nitrogen yearly.Recommendation and Outlook Successive land application of sewage sludge for at least three years followed by no sewage sludge application for at least two years may well be a good practice economically because it will boost and/or maintain sustainable forage productivity and at the same time minimize probable accumulation of nutrients, especially trace metals. Consecutive applications of sewage sludge may result in build up of some trace metals in some other states with initial high metallic content, but in this study, no detrimental effects on soil chemical properties were detected. The possibilities for economically sound application strategies are encouraging, but more and additional research is required to find optimal timing and rates that minimizes negative impacts on soil quality in particular or the environment in general. For proper utilization of sewage sludge, knowledge of the sewage sludges’ composition, the crop receiving it, are absolutely crucial, so that satisfactory types and rates are applied in an environmentally safe manner. There is still much to be learned from this study and this investigation needs to continue to determine whether the agricultural and ecological objectives are satisfied over the longer term.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

Effect of organic amendments on the mobility of trace elements in phytoremediated techno-soils: role of the humic substances

The efficiency of aided phytostabilization using organic amendments such as ramial chipped wood (RCW) and composted sewage sludge (CSS) was studied on contaminated techno-soils, on nine experimental plots. The objective was to characterize the role of fulvic (FA) and humic acids (HA) on the mobilization of trace elements, specifically As, Cu, Mo, Pb and Zn. Results showed that the addition of CSS increased the total organic carbon and nitrogen content more than with RCW and as a result, the C/N ratio in the CSS soil was higher than in the RCW and non-amended (NE) soil, reflecting the high decomposition of soil organic matter in the CSS soil compared with the other soils. The RCW and CSS amendments increased the hydrogen index (HI) values and the oxygen index (OI) values compared with the NE soil, especially for the soil treated with CSS which contained more aliphatic than aromatic compounds. The addition of CSS to the techno-soil significantly increased the percentage of C _org associated with the HA fractions compared with the RCW and NE soils. The soil amended with CSS showed the highest E ₄/E ₆ ratio and the lowest E ₂/E ₃ ratio of FA. Zn and As were more abundant in the FA fraction than in the HA fraction, whereas Pb, Cu and Mo were more associated to HA than to FA in the treated and untreated soils, which may explain the difference in their mobility and availability.     

Physicochemical soil parameters affecting sequestration and mycobacterial biodegradation of polycyclic aromatic hydrocarbons in soil

Six soils, obtained from grasslands and wooded areas in Northeastern Illinois, were physicochemically characterized. Measured parameters included total organic carbon (TOC) content, contents of humic acid, fulvic acid and humin, pore volume and pore size distribution, and chemical makeup of soil organic matter (determined using solid-state ¹³C-NMR). Moistened, gamma-sterilized soils were spiked with 200 ppm of either phenanthrene or pyrene (including ¹⁴C label); following 0, 40, or 120 days of aging, the contaminant-spiked soils were then inoculated with Mycobacterium austroafricanum strain GTI-23, and evolution of ¹⁴CO₂ was assessed over a 28-day period. Results for both phenanthrene and pyrene indicated that increased contact time led to increased sequestration and reduced biodegradation, and that TOC content was the most important parameter governing these processes. One soil, although only tested with phenanthrene, showed significantly lower-than-expected sequestration (higher-than-expected mineralization) after 40 days of aging, despite a very high TOC value (>24%). Because the level of sequestration in this soil was proportional to the others after 120 days of aging, this implies some difference in the temporal progression of sequestration in this soil, although not in its final result. The primary distinguishing feature of this soil was its considerably elevated fulvic acid content. Further experiments showed that addition of exogenous fulvic acid to a soil with very low endogenous humic acids/fulvic acids content greatly enhanced pyrene mineralization by M. austroafricanum. Extractabilities of 13 three- to six-ring coal tar PAHs in n-butanol from the six soils after 120 days of sequestration were strongly TOC-dependent; however, there was no discernible correlation between n-butanol extractability and mycobacterial PAH mineralization.     

Application of a battery of biotests for the determination of leachate toxicity to bacteria and invertebrates from sewage sludge-amended soil

The objective of the study was to determine the leachates toxicity from sewage sludge-amended soils (sandy and loamy). Samples originated from a plot experiment realized over a period of 29 months. Two types of soil were fertilized with sewage sludges at the dose of 3 % (90 t/ha). Soil samples were taken after 0, 7, 17, and 29 months from the application of sewage sludges. Leachates were obtained according to the EN 12457–2 protocol. The following commercial tests were applied for the estimation of the toxicity: Microtox (Vibrio fischeri), Microbial assay for toxic risk assessment (ten bacteria and one yeast), Protoxkit F? (Tetrahymena thermophila), Rotoxkit F? (Brachionus calyciflorus), and Daphtoxkit F? (Daphnia magna). The test organisms displayed varied toxicity with relation to the soils amended with sewage sludges. The toxicity of the leachates depended both on the soil type and on the kind of sewage sludge applied. Notable differences were also observed in the sensitivity of the test organisms to the presence of sewage sludge in the soil. The highest sensitivity was a characteristic of B. calyciflorus, while the lowest sensitivity to the presence of the sludges was revealed by the protozoa T. thermophila. Throughout the periods of the study, constant variations of toxicity were observed for most of the test organisms. The intensity as well as the range of those variations depended both on the kind of test organism and on the kind of sludge and soil type. In most cases, an increase of the toxicity of soils amended with the sewage sludges was observed after 29 months of the experiment.     

Phytoavaelability and extractability of copper and zinc in calcareous soil amended with composted Urban wastes

Abstract

A greenhouse experiment was conducted under simulated field conditions using large‐capacity plastic pots, filled each one with 25 kg of air‐dried calcareous soil. Besides the control, four treatments were prepared by applying separately two rates (20 and 80 Mg ha^‐1) of municipal solid waste (MSW) compost, and co‐composted municipal solid waste and sewage sludge (MSW‐SS). Lettuce was planted and harvested 2.5 months later. The application of composted urban wastes tended to increase Cu concentration in lettuce with respect to the control, but it was only significant when the higher rate of MSW compost was applied. The control showed values of Zn concentration in plant within a deficient range. In general, composted urban wastes treatments had increased Zn concentration values, which were within the sufficiency range. Both treatments with MSW compost increased Cu and Zn uptake in comparison with MSW‐SS co‐compost treatments. At the postharvest, all composted urban wastes treatments increased significantly DTPA‐extractable Cu content in soil with respect to the control; it was also significant the increase in AAAc‐EDTA‐extractable Cu in soil produced by the addition of the higher rate of MSW compost. The application of composted urban wastes increased significantly DTPA‐extractable and AAAc‐EDTA‐extractable Zn contents in soil versus the control, except for the lower rate of MSW‐SS co‐compost. The values of DTPA‐extractable/total ratio for Cu and Zn were under 10%, except for the treatment applying the higher rate of MSW compost which promoted higher values. The values of AAAc‐EDTA‐extractable/total ratio for Cu were above 10% in all treatments including the control. This tendency was also observed in AAAc‐EDTA‐extractable/total ratio for Zn when applying both rates of MSW compost or the higher rate of MSW‐SS co‐compost.     

Investigating roles of organic and inorganic soil components in sorption of polar and nonpolar aromatic compounds

The main objective of the present study was to assess the roles of various soil components in sorption of organic compounds differing in polarity. Removal of the whole soil organic matter decreased sorption by approximately 86% for nonpolar 1,3,5-trichlorobenzene (TCB), but only 34-54% for highly polar 1,3,5-trinitrobenzene (TNB); however, removal of the extractable humic/fulvic acids did not much affect sorption of the two sorbates. With normalization of solute hydrophobicity, TNB exhibits several orders of magnitude stronger sorption compared with TCB to maize burn residue (black carbon), extracted humic acid and Na⁺-saturated montmorillonite clay, suggesting specific sorptive interactions for TNB with the individual model soil components. It was proposed that sorption of TCB to the bulk soil was dominated by hydrophobic partition to the condensed, non-extractable fraction of organic matters (humin/kerogen and black carbon), while interactions with soil clay minerals were an important additional factor for sorption of TNB.