Biochar-based polymeric film as sustainable and efficient sorptive phase for preconcentration of steroid hormones in environmental waters and wastewaters.

BACKGROUND: The environmental impact of sample preparation should be minimized through simplification of the procedures and the use of natural, renewable and/or reusable materials. In such scenario, thin-film microextraction fulfils the former criteria, as it enables few steps and miniaturization, thus small amount of extraction phase. At the same time, the use of sorbents such as biochars obtained from biomass waste is even more promoted due to their availability at low cost and increased life-cycle in a circular economy vision. However, it is not always easy to combine these criteria in sample preparation. RESULTS: A thin film microextraction was developed for the determination of steroids in aqueous samples, entailing a membrane made of cellulose triacetate and a wood-derived biochar (Nuchar®) as carbon precursor. Different characterization techniques showed the successful preparation, whereas the sorption kinetics experiments demonstrated that biochar is responsible for the extraction with the polymer acting as a smart support. After a study about membranes' composition in terms of biochar amounts (4 %, 10 %, 16 % wt) and type of synthesis set up, the ceramic 3D-mold was selected, achieving reproducible and ready-to-use membranes with composition fixed as 10 %. Different elution conditions, viz. type and time of agitation, type, composition and volume of eluent, were evaluated. The final microextraction followed by HPLC-MS/MS quantification was successfully validated in river and wastewater treatment plant effluent samples in terms of accuracy (R% 64-123 %, RSD<19 % in river; R% 61-118 %, RSD <18 % in effluent, n = 4), sensitivity (MQLs 0.2-8.5 ng L-1) and robustness. SIGNIFICANCE: This novel biochar-based polymeric film proved to be a valid and sustainable sorbent, in terms of extraction capability, ease of preparation and greenness. By comparison with literature and the greenness evaluation with the most recent metric tools, this method expands the potential applicability of the thin-film microextraction and opens up innovative scenarios for sustainable procedures entailing the use of biochars entrapped in bio-polymers.

Competitive heavy metal adsorption on pinecone shells: Mathematical modelling of fixed-bed column and surface interaction insights.

Pinecone shells are assessed as a cost-effective biosorbent for the removal of metal ions Pb(II), Cu(II), Cd(II), Ni(II), and Cr(VI) in a fixed-bed column. Influent concentration, bed height, and flowrate are studied to improve efficiency. The breakthrough data is well fitted by the Sips adsorption model, suggesting a surface complexation mechanism, with maximum adsorption capacities of 11.1 mg/g for Cu(II) and 66 mg/g for Pb(II). In multimetal solutions, the uptake sequence at breakthrough and saturation is Pb(II) > Cu(II) > Cd(II). Characterization via FTIR and XRD reveals carboxyl and hydroxyl functional groups interacting with metal ions. Ca(II) does not compete with Pb(II), Cu(II), and Cd(II) adsorption, highlighting the ability of pinecone to adsorb heavy metals via surface complexation. Its application in the treatment of industrial effluents containing Cu(II), Ni(II), and Cr(VI) is explored. The study investigates bed media regeneration via eluting adsorbed metal ions with hydrochloric acid solutions. The potential of pinecone shells as an efficient biosorbent for removing toxic metal ions from industrial wastewater is emphasized. These findings enhance our understanding of the adsorption mechanism and underscore the fixed-bed column system's applicability in real-world scenarios, addressing environmental concerns related to heavy metal contamination of industrial effluents.

High-rate activated sludge at very short SRT: Key factors for process stability and performance of COD fractions removal.

In high-rate activated sludge (HRAS) processes, reducing the solid retention time (SRT) minimizes COD oxidation and allows to obtain the maximum energy recovery. The aim of this research was to operate a pilot plant with an automatic control strategy to assure the HRAS process stability and high COD fractions removal at very low SRT. This study combines simulation and experimental tools (pilot plant 35 m3·d - 1) operating at SRT (0.2 d), HRT (0.6 h) and DO (0.5 mg·L - 1) treating high-strength raw wastewater, at 18-26°C, at variable flow. The research includes the effects of temperature, influent concentration and MLSS reactor concentration over the sCOD, cCOD and pCOD removal. The study points out that the best parameter to control the HRAS at a low SRT is not strictly the SRT but rather the reactor MLSS concentration: operating at 2,000±200mg·L - 1 assured a stable process despite the large influents variation. Low SVI values of 50-70ml·g - 1 indicated the good settling properties of the biomass. With only a 6.9% COD oxidation, a high organic matter removal (57±9% for COD and 56±10% for BOD5), was reached. The high removal efficiencies for pCOD (74%) compared to the (29%) for sCOD and (12%) for cCOD also confirmed the importance of settling efficiency and stability in the HRAS. The direct correlation between COD influent and COD removal makes advisable to use the HRAS as a replacement of the primary clarifier. The HRAS acted efficiently as a filter for COD and pCOD peak loads and, in a lesser extent, for BOD5, while sCOD peaks were not buffered. The adopted model presented a good fit for COD fractions except for pCOD when the temperature exceeds 23 °C.

The core microbiome is responsible for volatile silicon and organic compounds degradation during anoxic lab scale biotrickling filter performance.

Volatile silicon compounds present in the biogas of anaerobic digesters can cause severe problems in the energy recovery systems, inducing costly damages. Herein, the microbial community of a lab-scale biotrickling filter (BTF) was studied while testing its biodegradation capacity on octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), in the presence of toluene, limonene and hexane. The reactor performance was tested at different empty bed residence times (EBRT) and packing materials. Community structure was analysed by bar-coded amplicon sequencing of the 16S rRNA gene. Microbial diversity and richness were higher in the inoculum and progressively decreased during BTF operation (Simpson's diversity index changing from 0.98-0.90 and Richness from 900 to 200 OTUs). Minimum diversity was found when reactor was operated at relatively low EBRT (7.3 min) using a multicomponent feed. The core community was composed of 36 OTUs (accounting for 55% of total sequences). Packing material played a key role in the community structure. Betaproteobacteriales were dominant in the presence of lava rock and were partially substituted by Corynebacteriales and Rhizobiales when activated carbon was added to the BTF. Despite these changes, a stable and resilient core microbiome was selected defining a set of potentially degrading bacteria for siloxane bioremoval as a complementary alternative to non-regenerative adsorption onto activated carbon.

Potential use of Methylibium sp. as a biodegradation tool in organosilicon and volatile compounds removal for biogas upgrading.

Organosilicon compounds are the most undesirable compounds for the energy recovery of biogas. These compounds are still resistant to biodegradation when biotechnologies are considered for biogas purification. Herein we isolated 52 bacterial species from anaerobic batch enrichment cultures (BEC) saturated with D4 and from an anaerobic lab-scale biotrickling filter (BTF) fed with a gas flow containing D4 as unique carbon source. Among those Methylibium sp. and Pseudomonas aeruginosa showed the highest capacity to remove D4 (53.04% ±â€¯0.03 and 24.42% ±â€¯0.02, respectively). Contrarily, co-culture evaluation treatment for the biodegradation of siloxanes together with volatile organic compounds removed a lower concentration of D4 compared to toluene and limonene, which were completely removed. Remarkably, the siloxane D5 proved to be more biodegradable than D4. Substrates removal values achieved by Methylibium sp. suggested that this bacterial isolate could be used in biological removal technologies of siloxanes.

Efficient removal of siloxanes and volatile organic compounds from sewage biogas by an anoxic biotrickling filter supplemented with activated carbon.

The removal of siloxanes (D4 and D5) and volatile organic contaminants (hexane, toluene and limonene) typically found in sewage biogas was investigated in a lab-scale biotrickling filter (BTF) packed with lava rock under anoxic conditions. Complete removal efficiencies for toluene and limonene were recorded at all empty bed residence time (EBRT) tested. The influence of EBRT was remarkable on the abatement of D5, whose removal decreased from 37% at 14.5 min to 16% at 4 min, while the removal of D4 and hexane remained below 16%. The packing material was supplemented with 20% of activated carbon aiming at increasing the mass transfer of the most hydrophobic pollutants. This strategy supported high removal efficiencies of 43 and 45% for hexane and D5 at the lowest EBRT. CO2 and silica were identified as mineralization products along with the presence of metabolites in the trickling solution such as dimethylsilanediol, 2-carene and α-terpinene.

Sewage biogas efficient purification by means of lignocellulosic waste-based activated carbons.

The present paper evaluates the efficiency of sustainable activated carbons obtained from the valorization of lignocellulosic waste in removing siloxanes and volatile organic compounds for the purification of anaerobic digester biogas. Pyrolized and non-pyrolized lignocellulosic residues generated in food and wood industries were used as precursor materials to obtain experimental adsorbents by a chemical activation process using several activating agents. The highest porosity was obtained by non-pyrolized residue activated by K2CO3 at 900 °C. The performance of the experimental materials was compared with that of commercial activated carbons in gas adsorption tests of siloxanes (octamethylcyclotetrasiloxane and hexamethyldisiloxane) and volatile organic compounds (toluene and limonene). The waste-based activated carbons developed in this work proved to be more efficient for the removal of both siloxanes and VOCs than the commercial samples in most of the conditions tested. Adsorption capacities correlated with porosity, while the more relevant pore size depends on the adsorbate.

Influencing factors on the removal of pharmaceuticals from water with micro-grain activated carbon.

The removal efficiency of 6 micro-grain AC (µGAC) was examined for 23 selected pharmaceutical compounds, usually found at trace level in municipal wastewater treatment plant (WWTP) effluents. Two different sets of experiments were carried out using distilled water and a real WWTP secondary effluent in order to understand the adsorption mechanisms of pharmaceuticals, including the role of the presence of background organic matter. Physical and chemical properties of µGACs and target pollutants were checked for their potential to predict the pharmaceutical removal. Textural properties of µGACs, and especially the mesopore volume, seemed to play the most important role during the adsorption without background organic matter whereas the chemistry of the µGACs, such as the presence of surface oxygen groups and the point of zero charge, could have more influence in the experiments with WWTP effluent water. Positively charged molecules are better adsorbed due to the influence of the background organic matter and the presence of oxygenated groups in the surface of the µGACs. The UV254 removal correlated well with the pharmaceutical removal and it is confirmed as an indicator to control the performance of pharmaceuticals adsorption with µGACs in tertiary treatment.

Regeneration of siloxane-exhausted activated carbon by advanced oxidation processes.

In the context of the biogas upgrading, siloxane exhausted activated carbons need to be regenerated in order to avoid them becoming a residue. In this work, two commercial activate carbons which were proved to be efficient in the removal of octamethylcyclotetrasiloxane (D4) from biogas, have been regenerated through advanced oxidation processes using both O3 and H2O2. After the treatment with O3, the activated carbon recovered up to 40% of the original adsorption capacity while by the oxidation with H2O2 the regeneration efficiency achieved was up to 45%. In order to enhance the H2O2 oxidation, activated carbon was amended with iron. In this case, the regeneration efficiency increased up to 92%.

Biogas upgrading: optimal activated carbon properties for siloxane removal.

A total of 12 commercial activated carbons (ACs) have been tested for the removal of octamethylcyclotetrasiloxane (D4) in dynamic adsorption experiments using different carrier gases and D4 concentrations. Characterization of the ACs included several physical and chemical techniques. The D4 adsorption capacities were strongly related with the textural development of the ACs. Results showed that the optimum adsorbent for D4 is a wood-based chemically activated carbon, which rendered an adsorption capacity of 1732 ± 93 mg g(-1) using 1000 ppm (v/v) of D4 with dry N2 as the carrier gas. When the concentration of D4 was lowered to typical values found in biogas, the adsorption capacity was halved. The presence of major biogas compounds (i.e., CH4 and CO2) and humidity further reduced the D4 adsorption capacity. The polymerization of D4 over the surface of all ACs was found to be relevant after prolonged contact times. The extent of this phenomenon, which may negatively affect the thermal regeneration of the AC, correlated reasonably well with the presence of phenolic and carboxylic groups on the carbon surfaces.