Occurrence and dissipation mechanisms of organic contaminants during sewage sludge anaerobic digestion: A critical review.

Sewage sludge, a complex mixture of contaminants and pathogenic agents, necessitates treatment or stabilization like anaerobic digestion (AD) before safe disposal. AD-derived products (solid digestate and liquid fraction) can be used as fertilizers. During AD, biogas is also produced, and used for energy purposes. All these fractions can be contaminated with various compounds, whose amount depends on the feedstocks used in AD (and their mutual proportions). This paper reviews studies on the distribution of organic contaminants across AD fractions (solid digestate, liquid fraction, and biogas), delving into the mechanisms behind contaminant dissipation and proposing future research directions. AD proves to be a relatively effective method for removing polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pharmaceuticals, antibiotic resistance genes and hydrocarbons. Contaminants are predominantly removed through biodegradation, but many compounds, especially hydrophobic (e.g. per- and polyfluoroalkyl substances), are also sorbed onto digestate particles. The process of sorption is suggested to reduce the bioavailability of contaminants. As a result of sorption, contaminants accumulate in the largest amount in the solid digestate, whereas in smaller amounts in the other AD products. Polar pharmaceuticals (e.g. metformin) are particularly leached, while volatile methylsiloxanes and polycyclic aromatic hydrocarbons, characterized by a high Henry's law constant, are volatilized into the biogas. The removal of compounds can be affected by AD operational parameters, the type of sludge, physicochemical properties of contaminants, and the sludge pretreatment used.

The impact of cyclic freezing and thawing (physical aging) on properties and polycyclic aromatic hydrocarbon content in biochars.

In this study, we investigated the effect of freeze-thaw cycles of sewage sludge (SSL)- and willow-derived biochars obtained at different temperatures on their physicochemical properties and total (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) content. In our research, we showed that the fate of Ctot PAHs depended on the type of SSL and may differ, which is determined mainly by the properties of the feedstock. The properties affect low-temperature SSL-derived biochars (500 °C) especially, in which the interactions based on π-π bonds between the PAHs and matrix during aging were weakened by newly created functional groups on the biochar surface. Additionally, the removal of ash or biochar particle fragmentation during aging increased the availability of solvent non-extractable PAHs, which resulted in an increase in the content of high molecular weight Ctot PAHs after aging. In turn, the Σ16 Cfree PAHs in biochars gradually decreased with their progressive surface functionalization, increase in specific surface area and pore volume and generally were independed on properties of feedstock and biochar. The obtained results evidence that the environmental risk associated with the use of SSL as a feedstock for biochar production is similar to or even lower than in the case when willow is used and depending on SSL type, the potential risk may be reduced or increased for low-temperature biochars.

The effect of biotransformation of sewage sludge- and willow-derived biochars by horseradish peroxidase on total and freely dissolved polycyclic aromatic hydrocarbon content.

This study analyzed the effect of enzymatic aging (horseradish peroxidase) of biochars on their content of solvent extractable (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbons (PAHs). Physicochemical properties and phytotoxicity of pristine and aged biochars were also compared. The study used biochars obtained at 500 or 700 °C from sewage sludges (SSLs) or willow. Compared to SSL-derived biochars, willow-derived biochars were more susceptible to enzymatic oxidation. Aging increased the specific surface area and pore volume of most SSL-derived biochars. An opposite direction, however, was found in the willow-derived biochars. Low-temperature biochars, regardless of their feedstock, underwent physical changes, such as removal of labile ash components or degradation of aromatic structures. The enzyme caused an increase in the content of Ctot light PAHs in biochars (by 34-3402 %) and heavy PAHs (≥4 rings) in the low-temperature SSL-derived biochars (by 46-713 %). In turn, the content of Cfree PAHs decreased in aged SSL-derived biochars (by 32-100 %). In the willow-derived biochars the bioavailability of acenaphthene increased (by 337-669 %), while the immobilization degree of some PAHs was lower (25-70 %) compared to the SSL-derived biochars (32-83 %). Nevertheless, aging positively affected the ecotoxicological properties of all biochars by increasing their stimulation effects or removing their phytotoxic effects on both Lepidium sativum seed germination and root growth. Significant relationships between the changes in Cfree PAH content, pH and salinity of SSL-derived biochars and seed germination/root growth inhibition were found. The study demonstrates that the risk associated with application of SSL-derived biochars, regardless of the type of SSL and pyrolysis temperature, can be lower in terms of Cfree PAHs than in the case of willow-derived biochars. Regarding to Ctot PAHs, high-temperature SSL-derived biochars are safer than low-temperature ones. In the case of application of high-temperature SSL-derived biochars, these with moderate alkalinity and salinity will not bring risks for plants.

Ecotoxicological characterization of engineered biochars produced from different feedstock and temperatures.

Biochar (BC) engineering, which has recently gained a lot of interest, allows designing the functional materials. BC modification improves the properties of pristine biochar, especially in terms of adsorption parameters. An interesting type of modification is the introduction of metals into the BC's structure. There is a knowledge gap regarding the effects of modified BC (e.g., BC-Mg, BC-Zn) on organisms. The aim of this study was the ecotoxicological evaluation of BC-Mg and BC-Zn composites, received under diverse conditions from willow or sewage sludge at 500 or 700 °C. The ecotoxicological tests with bacteria Vibrio fischeri (V. fischeri) and invertebrates Folsomia candida (F. candida) were applied to determine the toxicity of BC. The content of toxic substances (e.g., polycyclic aromatic hydrocarbons (PAHs), heavy metals (HMs), environmentally persistent free radicals (EPFRs)) in BC were also determined and compared with ecotoxicological parameters. The ecotoxicity of studied BCs depends on many variables: feedstock type, pyrolysis temperature and the modification type. The Zn and Mg modification reduced (from 28 to 63 %) the total Æ©16 PAHs content in willow-derived BCs while in SL-derived BCs the total Æ©16 PAHs content was even 1.5-3 times higher compared to pristine BCs. The Zn modified willow-derived BCs affected positively on F. candida reproduction but showed inhibition of luminescence V. fischeri. BC-Mg exhibited harmful effect to F. candida. The ecotoxicological assessment carried out sheds light on the potential toxicity of BC-Zn and BC-Mg composites, which are widely used in the removal of heavy metals, pharmaceuticals, dyes from waters and soils.

Mechanism of aging of biochars obtained at different temperatures from sewage sludges with different composition and character.

The aim of this study was to determine the effect of abiotic aging of sewage sludge (SSL)-derived biochars on their physicochemical properties and in consequence on their stability. Biochars produced at 500 or 700 °C from SSLs with a different composition and properties were incubated at different temperatures (-20, 4, 20, 60, and 90 °C) for 6 and 12 months. Pristine and aged biochars were characterized in terms of their composition and properties using a range of complementary methods. The results showed that SSL-derived biochars will not be as stable as previously thought in the long term. The stability of the SSL-derived biochars was closely related to the content and character of C. The biochars that had more C in their composition and, apart from aromatic C, also aliphatic matter/carbon substances deposited in surface pores (i.e. those produced from SSL with a lower initial ash content and a lower degree of aromaticity) were less stable than the biochars with a lower C content and a typically aromatic character of C (i.e. those derived from SSL with a higher initial ash content and a higher degree of aromaticity). Their oxidation led to partial mineralization of aliphatic chains or organic surface film and manifested itself in a greater changes in their properties. The low-temperature biochars (BC-500) with lower aromaticity were found to be more susceptible to oxidation than the high-temperature ones (BC-700) with higher aromaticity. The more aromatic structure of C limited access of O2 molecules to biochar interior, due to which the processes occurring during aging were concentrated in their surface layer and their properties were less change. It can therefore be concluded that pyrolysis of SSL with higher aromaticity and a lower organic content and higher pyrolysis temperatures will lead to obtaining more stable SSL-derived biochars.

Ecotoxicological assessment of sewage sludge-derived biochars-amended soil.

The study aimed to evaluate the ecotoxicity of soil (S) amended with biochars (BCKN) produced by the thermal conversion of sewage sludge (SSL) at temperatures of 500 °C, 600 °C, or 700 °C and SSL itself. The ecotoxicological tests were carried out on organisms representing various trophic levels (Lepidium sativum in plant, Folsomia candida in invertebrates, and Aliivibrio fischeri in bacteria). Moreover, the study evaluated the effects of three plants (Lolium perenne, Trifolium repens, and Arabidopsis thaliana) growing on BCKN700-amended soil on its ecotoxicological properties. The experiment was carried out for six months. In most tests, the conversion of sewage sludge into biochar caused a significant decrease in toxicity by adding it to the soil. The pyrolysis temperature directly determined this effect. The soil amended with the biochars produced at higher temperatures (600 °C and 700 °C) generally exhibited lower toxicity to the test organisms than the SSL. Because of aging, all the biochars lost their inhibition properties against the tested organisms in the solid-phase tests and had a stimulating influence on the reproductive ability of F. candida. With time, the fertilizing effect of the BCKN700 amended soil also increased. The aged biochars also did not have an inhibitory effect on A. fischeri luminescence in the leachate tests. The study has also demonstrated that the cultivation of an appropriate plant species may additionally reduce the toxicity of soil fertilized with biochar. The obtained results show that the conversion of sewage sludge to biochar carried out at an appropriate temperature can become a useful method in reducing the toxicity of the waste and while being safe for agricultural purposes.

Sewage sludge and solid residues from biogas production derived biochar as an effective bio-waste adsorbent of fulvic acids from water or wastewater.

Due to environmental concern, direct utilization of sewage sludge or residues from biogas production is restricted. Conversion of problematic bio-wastes into biochars can be a very effective solution. In the presented study, the adsorption of fulvic acids onto series of biochars produced from bio-wastes such as sewage sludge, residues from biogas production, and plant (Miscanthus sp.) were performed to examine the behavior of biochars in the environment and interactions with fulvic acids as the representatives of dissolved organic matter. The results clearly indicate that the highest excess of fulvic acids, 93-96 mg g-1, was chemisorbed onto biochar obtained specifically from sewage sludge. The mechanism of the adsorption was independent from applied biochar feedstock. Monolayer coverage was dominant onto all biochars. Generally, adsorption was assumed to be controlled by polar interactions between fulvic acids and the biochars or pre-adsorbed and residual fulvic acids molecules (which were dominant) and the strong π-π interactions. The obtained high values of the adsorption capacity of sewage sludge derived biochars confirmed that thermal treatment is a very effective tool of bio-waste management.

Biochars ages differently depending on the feedstock used for their production: Willow- versus sewage sludge-derived biochars.

The aim of this study was to determine the effect of abiotic aging of biochars under controlled laboratory conditions on its physicochemical properties and in consequence on their stability. Biochars (BCs) produced at 500 and 700 °C from willow or sewage sludge were incubated at different temperatures (-20, 4, 20, 60, or 90 °C) for 6 and 12 months. Pristine (i.e. immediately after their production) and aged BCs were characterized using a range of complementary methods. As a result of simulated temperature aging, there was a change in all biochar properties studied, with the direction of these changes being determined by both the type of feedstock and biochar production temperature. At all temperatures, aging was the most intense during the first 6 months and led to oxidation of the biochars and removal of the most labile components from them. The intensity of these processes increased with increasing aging temperature. Incubation of the biochars for another 6 months did not have such a significant effect on the biochar properties as that observed during the first months of incubation, which is evidence that the biochars had reached stability. The sewage sludge-derived biochars with a higher mineral content than the willow-derived biochars were less stable. The low-temperature biochars (BC-500) with lower aromaticity were more prone to abiotic oxidation than the high-temperature biochars (BC-700) with higher aromaticity and structurally ordered C. Based on this study, it can be concluded that aging induced changes will be specific for each biochar, i.e. they will depend on both the type of feedstock and pyrolysis temperature. Nonetheless, all biochars will be oxidized to a smaller or greater extent, which will result in an increase in the number of surface oxygen functional groups, an increased degree of their hydrophilicity and polarity, and a decrease in pH.

The convertion of sewage sludge to biochar as a sustainable tool of PAHs exposure reduction during agricultural utilization of sewage sludges.

There is a discussion in the literature whether PAHs introduced with biochar are safe and whether they are persistent in the environment. The persistence of PAHs (Ctot - total and Cfree - freely dissolved) in sewage sludge (SSL) or SSL-derived biochar-amended soils was investigated. Biochar were produced at 500, 600 and 700 °C. We also compared the persistence of PAHs in these experimental treatments depending on the plants cultivated (grass, clover and thale cress). We showed that the Ctot PAHs in the biochar-amended soils exhibited higher persistence than in the SSL-amended soil. The opposite trend was observed for Cfree PAHs. A higher reduction of Cfree PAHs was noted in the biochar-amended soils than in SSL-amended soil. The persistence of both Cfree and Ctot PAHs clearly varied between the biochars produced at different temperatures. It should be stated that despite that for biochar the persistence of Ctot PAHs is higher compared to SSL-amended soils, an opposite trend is observed for the fraction of Cfree (which is directly responsible for the toxic effect), and this entails a lower risk to the environment (lower mobility and bioavailability). The plants had a significant impact on Ctot PAHs content depending on the number of PAH rings.

Polycyclic aromatic hydrocarbons (PAHs) persistence, bioavailability and toxicity in sewage sludge- or sewage sludge-derived biochar-amended soil.

Soils can be contaminated with polycyclic aromatic hydrocarbons (PAHs) when either sewage sludge (SSL) or biochar (BC) are used. There are no comparative studies regarding the effects of soil amendment with SSL or BC on the persistence, bioavailability and toxicity of PAHs. This research compared the persistence of PAHs (based on the extractable content, Ctot) and their bioavailability (freely dissolved, Cfree) as well as the toxicity (solid phase: Phytotoxkit F with Lepidium sativum and the Collembolan test with Folsomia candida; leachates: Phytotestkit F with L. sativum and Microtox® with Aliivibrio fischeri) of soil amended with SSL or with SSL-derived BCs. BCs were produced from three different sewage sludges at a temperature of 500 °C. SSLs or BCs were added to the soil at a rate of 1% (30 t/ha). Adding SSL to the soil increased more the PAH content in it than after BC application, which was associated with a higher content of PAHs in SSL. Losses of Σ16 Ctot and Cfree PAHs were higher than those observed for biochar only in the case of one SSL. In the other cases, PAH losses were either higher for biochar or did not differ significantly between SSL and BC. On the other hand, the analysis of the individual groups of PAHs showed significant differences between SSL and BC, both for Ctot and Cfree. Nonetheless, these differences were largely driven by the type of sewage sludge and biochar. Only in the case of root growth inhibition the toxicity higher was for the SSL-amended soils than for the BC-amended ones. In the other cases, varying results were observed which were determined by the type of sewage sludge/biochar, similarly to PAH losses.

Adsorption capacity of phenanthrene and pyrene to engineered carbon-based adsorbents produced from sewage sludge or sewage sludge-biomass mixture in various gaseous conditions.

Adsorption of phenanthrene (PHE) and pyrene (PYR) by engineered carbon-based adsorbents produced from sewage sludge in an atmosphere of nitrogen (N2) or carbon dioxide (CO2) at temperatures of 500, 600, and 700 °C was investigated. The addition of willow to the SSL decreased the biochar adsorption capacity. However, there was an increase in the adsorption capacity after changing N2 to CO2. The addition of willow to SSL and the type of carrier gas affected the mechanism of adsorption. The adsorption of PHE and PYR on the SSL-derived adsorbents produced in N2 occurred through pore filling. The adsorption on the SSL-derived adsorbents with willow followed the mechanism of π-π electron-donor-acceptor (EDA) interactions and hydrophobic interactions. A similar mechanism was observed with regard to the biochars produced from SSL in atmosphere of CO2. For the SSL-derived adsorbents with willow in CO2, the adsorption mechanism was observed to vary between PHE and PYR.

Impact of ZnO and ZnS nanoparticles in sewage sludge-amended soil on bacteria, plant and invertebrates.

The effect of zinc oxide nanoparticles (ZnO NPs) and zinc sulfide nanoparticles (ZnS NPs) on the toxicity of sewage sludges in sewage sludge-amended soils was investigated with respect to plant- (Lepidium sativum) and soil- (Folsomia candida) species. The toxicity of porewater obtained from the tested soils towards Vibrio fischeri (Microtox®) was also investigated. Two sewage sludges (SSL1 and SSL2) with different organic matter content were amended with nanoparticles. Depending on the type of biotest and the type of sewage sludge, different effects of ZnO or ZnS NPs on the toxicity of sewage sludge-amended soil were observed. In general, ZnO and ZnS NPs stimulated root growth for SSL1 or reduced the harmful impact of SSL2 on the root growth of L. sativum roots. Greater stimulation or inhibition of root growth was observed for the ZnO than ZnS NPs. The unfavorable effect of ZnO/ZnS NPs on F. candida mortality and reproduction was observed at a concentration of ZnO/ZnS in sewage sludge ≥250 mg/kg. Generally, there were no significant differences between ZnO and ZnS NPs toxicity towards F. candida. Aging for 45 days of sewage sludge-amended soil containing NPs affected ZnO and ZnS NPs toxicity to all tested organisms. In the most cases, the toxicity decreased after 45 days of aging for plant (L. sativum) and invertebrates (F. candida). The toxicity of porewater to V. fischeri from sewage sludge-amended soil contains ZnO NPs did not change, while in the case of ZnS NPs, the toxicity increased after 45 days of aging.