Phosphorus speciation in sewage sludge and their ashes after incineration as a function of treatment processes.

Phosphorus (P) is a key component in agricultural fertilizers, but it is also a scarce resource, why its recycling has been thoroughly investigated and one promising resources is sewage sludge. Because of stricter regulations in terms of sludge disposal, thermal treatment (e.g. incineration) has become an attractive option. The incineration process alters the chemical speciation of P in favour to calcium-associated (apatite, apatite phosphorus (AP)) species, which is preferred for P recovery. In order to achieve qualitatively transformation, it is important to identify limiting or promoting factors. This study reports on the impact of iron, aluminium and calcium on the transformation of iron- and aluminium-phosphate (NAIP) to AP species, assessed by studying sludge and ash from 10 municipal wastewater treatment plants in Sweden. The effect of iron and aluminium added in the treatment processes was also evaluated. The obtained results show that high calcium concentration favours formation of AP species in both sludge and ashes, whereas high concentration of iron and aluminium favours formation of NAIP species in the sludge. The transformation from NAIP to AP species is hampered by aluminium, irrespectively of its origin, whereas no such correlations could be seen for iron. Therefore, in order to enable efficient P recovery from sewage sludge ash, the amount of aluminium added in the treatment process, as well as its concentration in influent streams to the treatment plants, must be limited.

Phosphorus speciation in sewage sludge from three municipal wastewater treatment plants in Sweden and their ashes after incineration.

Given the high efficiency in phosphorus removal at municipal wastewater treatment plants (MMWWTP), sewage sludge constitutes a promising resource for phosphorus (P) recovery. Sewage sludge is, however, a complex matrix and its direct use as fertiliser is limited by its content of metals/metalloids and organic pollutants. In order to increase its usability as a potential resource of P, there is a need for increased knowledge on phosphorus speciation in these matrices. The sludge composition is highly influenced by local conditions (i.e. wastewater composition and treatment method), and it is therefore important to study sludge from several MMWWTPs. In this study, three different protocols for sequential extraction were utilised to investigate the chemical speciation of phosphorus in sludge from three different MMWWTP sludges in Sweden, as well as in corresponding ashes following incineration. The results showed that the total amounts of phosphorus ranged from 26 to 32 mg g-1 sludge (dry weight), of which 79-94% was inorganically bound (IP). In the sludge, 21-30% of the IP was associated with calcium (Ca-P), which is the preferred species for fertiliser production. Following incineration, this fraction increased to 54-56%, mainly due to transformation of iron-associated phosphorus (Fe-P), while aluminium-associated species of phosphorus (Al-P) remained unaltered. The results from this study confirm that incineration is a suitable treatment for sewage sludge in terms of potential phosphorus recovery.

Re-cycling of remediated soil--evaluation of leaching tests as tools for characterization.

In Sweden, leaching tests with deionized water (D.W.) are utilized in risk assessment of materials entering landfills, but implementation of these results to evaluate the risk of spreading of pollutants in the environment is difficult. One problem is that most leaching procedures only consider heavy metals release, whereas organic pollutants are left out. The aim of the present study was to assess the possible pollutant mitigation in four remediated soils, three with heavy metals and one with polycyclic aromatic hydrocarbons (PAH) contamination. The mitigation was evaluated by standardized batch and column leaching tests utilizing three different leaching solutions: D.W., a weak ionic solution (0.001 M CaCl(2)) and an artificially made soil water (ASW). In general, batch leaching tests implied larger contaminant removal than column leaching test, possibly due to the more rough treatment of the soil particles, and guidelines would at times be exceeded by the batch leaching test but not by column leaching tests. Utilization of CaCl(2) was found to release less heavy metal than D.W., whereas the metals mobilized by ASW were removed from solution by the filtration of soil leachates. Low molecular weight PAH was most efficiently mobilized by CaCl(2), while D.W. worked better for high molecular weight PAH. Despite very low initial PAH-concentrations, tap- and groundwater criteria were exceeded by all leaching solutions.

Remediation of heavy metal contaminated soil washing residues with amino polycarboxylic acids.

Removal of Cu, Pb, and Zn by the action of the two biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS) and methylglycinediacetic acid (MGDA), as well as citric acid, was tested. Three soil samples, which had previously been treated by conventional soil washing (water), were utilized in the leaching tests. Experiments were performed in batches (0.3 kg-scale) and with a WTC-mixer system (Water Treatment Construction, 10 kg-scale). EDDS and MGDA were most often equally efficient in removing Cu, Pb, and Zn after 10-60 min. Nonetheless, after 10d, there were occasionally significant differences in extraction efficiencies. Extraction with citric acid was generally less efficient, however equal for Zn (mainly) after 10d. Metal removal was similar in batch and WTC-mixer systems, which indicates that a dynamic mixer system could be used in full-scale. Use of biodegradable amino polycarboxylic acids for metal removal, as a second step after soil washing, would release most remaining metals (Cu, Pb and Zn) from the present soils, however only after long leaching time. Thus, a full-scale procedure, based on enhanced metal leaching by amino polycarboxylic acids from soil of the present kind, would require a pre-leaching step lasting several days in order to be efficient.

Laboratory and pilot scale soil washing of PAH and arsenic from a wood preservation site: changes in concentration and toxicity.

Soil washing of a soil with a mixture of both polycyclic aromatic hydrocarbons (PAH) and As was evaluated in laboratory and pilot scale, utilizing both single and mixtures of different additives. The highest level of decontamination was achieved with a combination of 0.213 M of the chelating agent MGDA and 3.2 x CMC* of a non-ionic, alkyl glucoside surfactant at pH 12 (Ca(OH)(2)). This combination managed to reach Swedish threshold values within 1 0 min of treatment when performed at elevated temperature (50 degrees C), with initial contaminant concentrations of As=105+/-4 mg/kg and US-EPA PAH(16)=46.0+/-2.3mg/kg. The main mechanisms behind the removal were the pH effect for As and a combination of SOM ionization as a result of high pH and micellar solubilization for PAHs. Implementation of the laboratory results utilizing a pilot scale equipment did not improve the performance, which may be due to the shorter contact time between the washing solution and the particles, or changes in physical characteristics of the leaching solution due to the elevated pressure utilized. The ecotoxicological evaluation, Microtox, demonstrated that all soil washing treatments increased the toxicity of soil leachates, possibly due to increased availability of contaminants and toxicity of soil washing solutions to the test organism.

AhR agonist and genotoxicant bioavailability in a PAH-contaminated soil undergoing biological treatment.

BACKGROUND, AIM, AND SCOPE: Degradation of the 16 US EPA priority PAHs in soil subjected to bioremediation is often achieved. However, the PAH loss is not always followed by a reduction in soil toxicity. For instance, bioanalytical testing of such soil using the chemical-activated luciferase gene expression (CALUX) assay, measuring the combined effect of all Ah receptor (AhR) activating compounds, occasionally indicates that the loss of PAHs does not correlate with the loss of Ah receptor-active compounds in the soil. In addition, standard PAH analysis does not address the issue of total toxicant bioavailability in bioremediated soil. MATERIALS AND METHODS: To address these questions, we have used the CALUX AhR agonist bioassay and the Comet genotoxicity bioassay with RTL-W1 cells to evaluate the toxic potential of different extracts from a PAH-contaminated soil undergoing large-scale bioremediation. The extracts were also chemically analyzed for PAH16 and PCDD/PCDF. Soil sampled on five occasions between day 0 and day 274 of biological treatment was shaken with n-butanol with vortex mixing at room temperature to determine the bioavailable fraction of contaminants. To establish total concentrations, parts of the same samples were extracted using an accelerated solvent extractor (ASE) with toluene at 100 degrees C. The extracts were tested as inducers of AhR-dependent luciferase activity in the CALUX assay and for DNA breakage potential in the Comet bioassay. RESULTS: The chemical analysis of the toluene extracts indicated slow degradation rates and the CALUX assay indicated high levels of AhR agonists in the same extracts. Compared to day 0, the bioavailable fractions showed no decrease in AhR agonist activity during the treatment but rather an up-going trend, which was supported by increasing levels of PAHs and an increased effect in the Comet bioassay after 274 days. The bio-TEQs calculated using the CALUX assay were higher than the TEQs calculated from chemical analysis in both extracts, indicating that there are additional toxic PAHs in both extracts that are not included in the chemically derived TEQ. DISCUSSION: The response in the CALUX and the Comet bioassays as well as the chemical analysis indicate that the soil might be more toxic to organisms living in soil after 274 days of treatment than in the untreated soil, due to the release of previously sorbed PAHs and possibly also metabolic formation of novel toxicants. CONCLUSIONS: Our results put focus on the issue of slow degradation rates and bioavailability of PAHs during large-scale bioremediation treatments. The release of sorbed PAHs at the investigated PAH-contaminated site seemed to be faster than the degradation rate, which demonstrates the importance of considering the bioavailable fraction of contaminants during a bioremediation process. RECOMMENDATIONS AND PERSPECTIVES: It has to be ensured that soft remediation methods like biodegradation or the natural remediation approach do not result in the mobilization of toxic compounds including more mobile degradation products. For PAH-contaminated sites this cannot be assured merely by monitoring the 16 target PAHs. The combined use of a battery of biotests for different types of PAH effects such as the CALUX and the Comet assay together with bioavailability extraction methods may be a useful screening tool of bioremediation processes of PAH-contaminated soil and contribute to a more accurate risk assessment. If the bioremediation causes a release of bound PAHs that are left undegraded in an easily extracted fraction, the soil may be more toxic to organisms living in the soil as a result of the treatment. A prolonged treatment time may be one way to reduce the risk of remaining mobile PAHs. In critical cases, the remediation concept might have to be changed to ex situ remediation methods.