Phosphorus recovery from aqueous product of hydrothermal carbonization of cow manure.

The work studies the recovery of nutrients (phosphorus and nitrogen) from the process water of acid-assisted hydrothermal carbonization (HTC) of cow manure. Three organic acids (formic acid, oxalic acid, and citric acid) and sulfuric acid were evaluated as additives in HTC. Using 0.3 M sulfuric acid, more than 99% of phosphorus and 15.6% of nitrogen from manure are extracted and dissolved during HTC at 170 °C with 10 min reaction time in a batch reactor. Nutrients (mainly phosphorus) were recovered through precipitation from process water by raising the ionic strength of the solution by addition of salts of magnesium and ammonia, and by raising the pH to 9.5. Subsequently, phosphorus-rich solids were recovered containing almost all (greater than 95%) of the dissolved phosphorus in the sulfuric and formic acid assisted runs. Morphology and qualitative chemical analysis of the precipitates were determined. It is shown by XRD that the precipitate formed from process water generated by HTC with oxalic acid is crystalline, although the diffraction pattern could not be matched with any expected substance.

Life cycle assessment of a novel strategy based on hydrothermal carbonization for nutrient and energy recovery from food waste.

In this work, a novel strategy for food waste valorization was evaluated from an environmental life-cycle perspective. A system based on acid-assisted hydrothermal carbonization of food waste combined with the exploitation of hydrochar by combustion and process water through nutrient recovery stage and subsequent anaerobic digestion, was assessed and compared with stand-alone anaerobic digestion as the reference system. This combination of processes aims to recover both nutrients in a stage of struvite precipitation from process water and energy through hydrochar and biogas combustion. Both systems were modeled in Aspen Plus® to identify and quantify their most relevant input and output flows and subsequently evaluate their environmental performance through the life cycle assessment methodology. The novel combined system was found to generally involve a more favorable environmental performance than the reference stand-alone configuration, which would be closely linked to the substitution of hydrochar for fossil fuels. In addition, the impacts associated with soil application of the struvite produced in the integrated process would also be reduced compared to the use of the digestate generated in the stand-alone anaerobic digestion process. Following these results and the evolving regulatory framework for biomass waste management, mainly in the field of nutrient recovery, combined process based on acid-assisted hydrothermal treatment plus nutrient recovery stage and anaerobic digestion is concluded to be a promising circular economy concept for food waste valorization.

Acid-mediated hydrothermal treatment of sewage sludge for nutrient recovery.

Hydrothermal carbonization allows material valorization and energy recovery from wet biomass waste. In this study, the hydrothermal treatment of dewatered waste-activated sludge (DWAS) was evaluated at several temperatures (170-230 °C) and reaction times (5-60 min) in an acid-free medium or in media such as citric acid or HCl (0.1-0.5 mol/L). Compared with the DWAS, an increase in the fixed carbon content (>45 wt%) and heating value (18.9-22.9 MJ/kg) was observed in the hydrochar; however, their ash content remained high, which is the main drawback hindering their direct use as a biofuel. The addition of acids during hydrothermal treatment favored the solubilization of N and P in the process water, which required strict control of the reaction time to avoid the recrystallization of P in the hydrochar. Under optimum operating conditions (230 °C, 15 min, 0.5 mol/L HCl), 94 % of P (as of PO4) and almost 100 % of N (14 % as NH4-N) present in the feedstock were concentrated in the process water.

Energy recovery from food waste and garden and park waste: Anaerobic co-digestion versus hydrothermal treatment and anaerobic co-digestion.

The feasibilities of the anaerobic co-digestion of two of the most relevant biowastes, food waste and garden and park waste, were evaluated and compared with the hydrothermal treatment of each waste and the anaerobic co-digestion of raw biowastes with the process water generated. The effects on the process stability and energy recovery were also analyzed. Anaerobic digestion was the best option for food waste treatment from an energetic point of view, with 81% recovery of the energy stored in the feedstock, while the highest energy recovery from garden and park waste was obtained for the solid fraction generated from hydrothermal treatment (85.5%). In addition, the anaerobic co-digestion of food waste with 5% of the process water generated from garden and park waste showed a similar energy recovery to that of food waste only (∼80%), thus improving the biological stability of the process.

Improved energy recovery from food waste through hydrothermal carbonization and anaerobic digestion.

Here we studied energy valorization of food waste by hydrothermal carbonization coupled with anaerobic digestion. Hydrothermal treatment was carried out at 200 °C and 230 °C for 1 h, obtaining hydrochar with properties suitable for solid biofuel according to ISO/TS 17225-8. The increase in temperature improved the fuel properties of hydrochar (higher heating value 20.3 and 23.7 MJ kg-1, fuel ratio 0.33 and 0.37, energy density 1.07 and 1.25). The anaerobic digestion of process water achieved methane yields around 150 mL CH4 STP g-1 CODadded and made it possible to remove some specific recalcitrant compounds, such as 2-methylpyridine and 2-ethyl-3-methylpyrazine. Energy recovery from hydrochar and process water seems to be an interesting alternative way to sustain the process energetically and economically, despite the significant energy inputs required for hydrothermal carbonization.

Fate of nutrients during hydrothermal treatment of food waste.

Hydrothermal carbonization was evaluated as a food waste valorization strategy to obtain hydrochar and recover nutrients. In the hydrothermal treatment, the temperature (170-230 °C), reaction time (5-60 min), and addition of HCl (0.1-0.5 M) during the reaction were analyzed. Compared to the feedstock, hydrochar showed an increase in fixed carbon (greater than 45%) and a decrease in ash content (<7%), along with a higher heating value (18.6-26.2 MJ/kg), which would allow for its application as a biofuel for industry according to ISO/TS 17225-8. The hydrochar obtained using plain carbonization showed 75% P and 40% N of the feedstock content, whereas the HCl-mediated treatment (0.5 M) solubilized most of the P, K, and N in the process water (98% P as PO4-P, 98% K, and the total N content as NH4-N (16%) and organic-N) operating at 170 °C for 60 min.

Sono- and photoelectrocatalytic processes for the removal of ionic liquids based on the 1-butyl-3-methylimidazolium cation.

In this work, sono- and photoelectrolysis of synthetic wastewaters polluted with the ionic liquids 1-Butyl-3-methylimidazolium acetate (BmimAc) and chloride (BmimCl) were investigated with diamond anodes. The results were compared to those attained by enhancing bare electrolysis with irradiation by UV light or with the application of high-frequency ultrasound (US). Despite its complex heterocyclic structure, the Bmim+ cation was successfully depleted with the three technologies that were tested and was mainly transformed into four different organic intermediates, an inorganic nitrogen species and carbon dioxide. Regardless of the technology that was evaluated, removal of the heterocyclic ring is much less efficient (and much slower) than oxidation of the counter ion. In turn, the counter ion influences the rate of removal of the ionic liquid cation. Thus, the electrolysis and photoelectrolysis of BmimAc are much less efficient than sonoelectrolysis, but their differences become much less important in the case of BmimCl. In this later case, the most efficient technology is photoelectrolysis. This result is directly related to the generation of free radicals in the solution by irradiation of the electrochemical system with UV light, which contributes significantly to the removal of Bmim+.

Anaerobic co-digestion of the aqueous phase from hydrothermally treated waste activated sludge with primary sewage sludge. A kinetic study.

The mesophilic anaerobic co-digestion of the liquid fraction from hydrothermal carbonization (LFHTC) of dewatered waste activated sludge with primary sewage sludge (PSS) has been studied. Mixtures of different composition (25, 50 and 75% of LFHTC on a chemical oxygen demand (COD) basis), as well as the individual substrates, have been tested using two inocula (flocculent (FS) and granular (GS) sludges). Methane production decreased as the LFHTC/PSS ratio increased, which can be related to the presence of recalcitrant compounds in the LFHTC, such as alkenes, phenolics, and other oxygen- and nitrogen-bearing aromatics hard-to-degrade through anaerobic digestion. Methane yield reached 248 ±â€¯11 mL CH4 STP/g CODadded with the GS inoculum and 25% LFHTC. A 74 and a 30% increase of methane production was achieved in the 25% LFHTC runs respect to the obtained in the similar experiments with 100% LFHTC, using the FS and GS inocula, respectively. In those late runs, the COD was reduced more than 86%, with a negligible concentration of total volatile fatty acids. With both inocula, total Kjeldahl nitrogen hydrolysis increased as the LFHTC to PSS mixture ratio decreased, reaching values higher than 79% at the end of the experiments. Methane yield values fitted well the first-order, Cone and Weibull kinetic models for both inocula. Significant differences in the kinetic constant values, ranging from 0.100 to 0.168 d-1 and 0.059-0.068 d-1, were found with the FS and GS inocula, respectively. The results obtained support the potential integration of HTC of dewatered waste activated sludge in wastewater treatment plants.

Removal of imidazolium-based ionic liquid by coupling Fenton and biological oxidation.

In this work, we assessed the potential of combining Fenton´s reagent and biological oxidation for removing the imidazolium-based ionic liquid 1-Ethyl-3-methylimidazolium chloride (EmimCl). Fenton-like oxidation was conducted at variable H2O2 doses from 20 to 100% the stoichiometric value as calculated from the theoretical chemical oxygen demand (COD). The stoichiometric H2O2 dose afforded Total Organic Carbon (TOC) conversion and COD removal of 50 and 62%, respectively. Identifying the reaction by-products formed at low hydrogen peroxide doses allowed a plausible pathway for EmimCl oxidation to be proposed. The effluents from Fenton-like oxidation at substoichiometric H2O2 doses were less ecotoxic and more biodegradable than was the parent ionic liquid. The effluent from Fenton-like oxidation with the 60% H2O2 dose (TOC conversion ≅ 41%, COD removal ≅ 31%) was subsequently subjected to an effective biological treatment that allowed complete removal of the starting compound, increased its ecotoxicity to a low-moderate level and rendered it acceptably biodegradable. Biological oxidation was performed in 8-h and 12-h cycles in a sequencing batch reactor. Combining Fenton and biological oxidation of EmimCl afforded TOC conversion and COD removal of around 90%.

Removal of imidazolium- and pyridinium-based ionic liquids by Fenton oxidation.

The oxidation of imidazolium (1-hexyl-3-methylimidazolium chloride, HmimCl) and pyridinium (1-butyl-4-methylpyridinium chloride, BmpyrCl) ionic liquids (ILs) by Fenton's reagent has been studied. Complete conversion was achieved for both ILs using the stoichiometric H2O2 dose at 70 °C, reaching final TOC conversion values around 45 and 55% for HmimCl and BmpyrCl, respectively. The decrease in hydrogen peroxide dose to substoichiometric concentrations (20-80% stoichiometric dose) caused a decrease in TOC conversion and COD removal and the appearance of hydroxylated oxidation by-products. Working at these substoichiometric H2O2 doses allowed the depiction of a possible degradation pathway for the oxidation of both imidazolium and pyridinium ILs. The first step of the oxidation process consisted in the hydroxylation of the ionic liquid by the attack of the ·OH radicals, followed by the ring-opening and the formation of short-chain organic acids, which could be partially oxidized up to CO2 and H2O. At H2O2 doses near stoichiometric values (80%), the resulting effluents showed non-ecotoxic behaviour and more biodegradable character (BOD5/COD ratio around 0.38 and 0.58 for HmimCl and BmpyrCl, respectively) due to the formation of short-chain organic acids. Graphical abstract ᅟ.

Electrolysis with diamond anodes: Eventually, there are refractory species!

In this work, synthetic wastewater polluted with ionic liquid 1-butyl-3-methylimidazolium (Bmim) bis(trifluoromethanesulfonyl)imide (NTf2) undergoes four electrolytic treatments with diamond anodes (bare electrolysis, electrolysis enhanced with peroxosulfate promoters, irradiated with UV light and with US) and results obtained were compared with those obtained with the application of Catalytic Wet Peroxide Oxidation (CWPO). Despite its complex heterocyclic structure, Bmim+ cation is successfully depleted with the five technologies tested, being transformed into intermediates that eventually can be mineralized. Photoelectrolysis attained the lowest concentration of intermediates, while CWPO is the technology less efficient in their degradation. However, the most surprising result is that concentration of NTf2- anion does not change during the five advanced oxidation processes tested, pointing out its strong refractory character, being the first species that exhibits this character in wastewater undergoing electrolysis with diamond. This means that the hydroxyl and sulfate radicals mediated oxidation and the direct electrolysis are inefficient for breaking the C-S, C-F and S-N bounds of the NTf2- anion, which is a very interesting mechanistic information to understand the complex processes undergone in electrolysis with diamond.

Assessment of toxicity and biodegradability on activated sludge of priority and emerging pollutants.

Several methods for evaluating the toxicity and biodegradability of hazardous pollutants (chlorinated compounds, chemical additives and pharmaceuticals) have been studied in this work. Different bioassays using representative bacteria of marine and terrestrial ecosystems such as Vibrio fischeri and Pseudomonas putida have been used to assess the ecotoxicity. Activated sludge was used to analyse the effect of those pollutants in a biological reactor of a sewage treatment plant (STP). The results demonstrate that none of the compounds is toxic to activated sludge, except ofloxacin to P. putida. The additives tested can be considered moderately toxic according to the more sensitive V. fischeri assays, whereas the EC50 values of the pharmaceuticals depend on the specific microorganism used in each test. Regarding the biodegradability, respirometric measurements were carried out for fast biodegradability assessment and the Zahn-Wellens test for inherent biodegradability. The evolution of the specific oxygen uptake rate (SOUR) showed that only diethyl phthalate was easily biodegradable and acetylsalicylic acid was partially biodegradable (98% and 65% degradation, respectively). The persistence of dichloromethane, ofloxacin and hidrochlorothiazide was confirmed along the 28 days of the Zahn-Wellens test whereas 1,1,1-trichloroethane showed inherent biodegradability (74% removal). Most of the chlorinated compounds, pharmaceuticals, bisphenol A and ethylenediaminetetraacetic acid were partially degraded in 28 d with total organic carbon (TOC) reduction ranging from 21% to 51%. Sulphamethoxazole showed certain biodegradation (50% removal) with TOC decrease around 31%, which indicates the formation of non-biodegradable by-products.

Harmonization of the quantitative determination of volatile fatty acids profile in aqueous matrix samples by direct injection using gas chromatography and high-performance liquid chromatography techniques: Multi-laboratory validation study.

The performance parameters of volatile fatty acids (VFAs) measurements were assessed for the first time by a multi-laboratory validation study among 13 laboratories. Two chromatographic techniques (GC and HPLC) and two quantification methods such as external and internal standard (ESTD/ISTD) were combined in three different methodologies GC/ESTD, HPLC/ESTD and GC/ISTD. Linearity evaluation of the calibration functions in a wide concentration range (10-1000mg/L) was carried out using different statistical parameters for the goodness of fit. Both chromatographic techniques were considered similarly accurate. The use of GC/ISTD, despite showing similar analytical performance to the other methodologies, can be considered useful for the harmonization of VFAs analytical methodology taking into account the normalization of slope values used for the calculation of VFAs concentrations. Acceptance criteria for VFAs performance parameters of the multi-laboratory validation study should be established as follows: (1) instrument precision (RSDINST≤1.5%); (2) linearity (R(2)≥0.998; RSDSENSITIVITY≤4%; REMAX≤8%; REAVER≤ 3%); (3) precision (RSD≤1.5%); (4) trueness (recovery of 97-103%); (5) LOD (≤3mg/L); and (6) LOQ (10mg/L).

Treatment of cosmetic wastewater by a full-scale membrane bioreactor (MBR).

This work evaluates the treatment of wastewater from a personal care products factory by a full-scale side-stream membrane bioreactor (MBR) intermittently fed. The wastewater contained particulate and soluble chemical oxygen demand (COD) which is partially removed by physicochemical pretreatment. Steady removal efficiencies above 98 % were achieved for BOD5, COD and suspended solids. Fats, oils and grease present in the raw wastewater were also successfully removed. The MBR was operated at an average permeate flux of 12 L/m2 · h (LMH) working at a transmembrane pressure of 272 ± 97 mbar. The soluble microbial products concentration remained fairly stable at 175 ± 25 and 85 ± 15 mg/L for proteins and carbohydrates, respectively. This maintained the filtration characteristics of the mixed liquor unaltered over a long-term basis, which was evidenced by a constant permeability of 43 ± 19 LMH/bar. Most of the trace organics detected in the wastewater were completely removed and only some fragrances were detected in the permeate at trace concentrations.

Degradation of chlorophenoxy herbicides by coupled Fenton and biological oxidation.

A combined treatment for the degradation of the chlorophenoxy herbicides 2,4-D and MCPA in water by means of Fenton and biological oxidation has been studied. The chemical oxidation step was necessary to achieve an efficient removal of these pollutants due to their toxicity and low biodegradability. Aqueous herbicide solutions (180mgL(-1)) were subjected to Fenton oxidation upon different H2O2 doses (from the theoretical stoichiometric amount referred to initial COD to 20% of this value). The toxicity and biodegradability tests of the Fenton effluents suggested that the ones resulting upon treatment with 80% and 60% of stoichiometric H2O2 were the optimal for subsequent biological treatment dealing with 2,4-D and MCPA, respectively. These effluents were treated in a sequencing batch reactor achieving nearly 90% conversion of organic matter measured as COD.

Enhancement of cometabolic biodegradation of 4-chlorophenol induced with phenol and glucose as carbon sources by Comamonas testosteroni.

The biological degradation of phenol and 4-chlorophenol (4-CP) by Comamonas testosteroni CECT 326T has been studied. Phenol and 4-CP were treated alone as a sole carbon and energy source, but only phenol was completely degraded by C. testosteroni. Since the presence of cosubstrates can enhance the toxic compounds removal by pure cultures, phenol and glucose were added as growth substrates for cometabolic transformation of 4-CP. High efficiencies were obtained in all the experiments carried out in presence of both cosubstrates. In spite of the fact that the addition of glucose reduced the lag phase of 4-CP removal, lower phenol concentrations were required to obtain the same degradation efficiencies. The cometabolic transformation of 4-CP was closely related with the extent of phenol removal. The values of the 4-CP/biomass concentration ratio (S/X) obtained for discriminating between complete (S/X ≤ 0.11) and partial 4-CP (S/X ≥ 0.31) transformation showed a narrower range than that reported in the literature. The extent of the cometabolic 4-CP transformation in the presence of phenol could be further enhanced by using glucose as an additional carbon and energy source. However, no significant influence of glucose concentration on 4-CP removal was observed over the concentration range studied.