Environmental Life Cycle Assessment of Hydrothermal Carbonization of Sewage Sludge and Its Products Valorization Pathways.

Abstract: This study is aimed at evaluating through Life Cycle Assessment (LCA) the environmental performances of an integrated system of an existing Water Resources Recovery Facility (WRRF) and a hypothetical hydrothermal carbonization (HTC) plant applied to the generated sewage sludge (SS). Beside the valorisation of the solid product (hydrochar, HC) as a fuel substituting lignite, the possibility to valorize also the liquid fraction (process water, PW) derived by the HTC, by anaerobic digestion to produce biogas, is here proposed and analysed. Additionally, phosphorus recovery from HC, prior its use, by acid leaching with nitric acid is also suggested and evaluated. Thus, four integrated scenarios, based on SS carbonization, are proposed and compared with the current SS treatment, based on composting outside of the WRRF (Benchmark scenario). The proposed scenarios, based on HTC, show improved performances with respect to the benchmark one, for thirteen of sixteen considered impact indicators. For the Climate Change (CC) indicator, the two HTC scenarios are able to reduce the impacts up to - 98%, with respect to the Benchmark. Further, the introduction of anaerobic digestion of PW proves to reduce impacts more than other configurations in eleven on sixteen impact categories. On the contrary, the introduction of phosphorus recovery process negatively affects the values for most of indicators. Thus, possible solutions to improve the integration of this process are outlined (e.g., the use of sulfuric acid instead of nitric one, or the application of a different ratio between solid and acidified solution during acid leaching of HC to recover phosphorus). Supplementary Information: The online version contains supplementary material available at 10.1007/s12649-022-01821-x.

Inhibitory effects of veterinary antibiotics on anammox activity: short- and long-term tests.

The suitability of the anammox process for the treatment of swine digester liquor was assessed through the evaluation of the short- and long-term inhibitory effect of three veterinary antibiotics commonly administered to Italian swine livestock. The toxicity of doxycycline, tiamulin and enrofloxacin was evaluated through batch tests designed to estimate specific anammox activity. Moreover, the short-term toxicity of combined concentrations of doxycycline and enrofloxacin was evaluated so as to verify whether a synergistic effect could be established. According to the inhibition recorded in the presence of the maximum antibiotics concentrations predicted for digester liquor, target compounds do not seem to represent a real hazard for anammox bacteria because at those concentration levels, the activity was just slightly reduced. Moreover, in granular systems, inhibition could be easily counterbalanced by increasing the biomass concentration in the reactor, thus assuring the design treatment capacity for antibiotic-rich wastewaters.

Multi-stage constructed wetland systems for municipal wastewater treatment.

In the present paper the detailed design and performances of two municipal wastewater treatment plants, a four-stage constructed wetlands (CW) system located in the city of Dicomano (about 3,500 inhabitants) in Italy, and a three-stage CW system for the village of Chorfech (about 500 inhabitants) in Tunisia, are presented. The obtained results demonstrate that multi-stage CWs provide an excellent secondary treatment for wastewaters with variable operative conditions, reaching also an appropriate effluent quality for reuse. Dicomano CWs have shown good performances, on average 86% of removal for the Organic Load, 60% for Total Nitrogen (TN), 43% for Total Phosphorus (TP), 89% for Total Suspended Solids (TSS) and 76% for Ammonium (NH4(+)). Even the disinfection process has performed in a very satisfactory way, reaching up to 4-5 logs of reduction of the inlet pathogens concentration, with an Escherichia coli average concentration in the outlet often below 200 UFC/100 mL. The mean overall removal rates of the Chorfech CWs during the monitored period have been, respectively, equal to 97% for TSS and Biochemical Oxygen Demand (BOD5), 95% for Chemical Oxygen Demand (COD), 71% for TN and 82% for TP. The observed removal of E. coli by the CW system was in this case 2.5 log units.

Inhibition effect of swine wastewater heavy metals and antibiotics on anammox activity.

The feasibility of anaerobic ammonium oxidation (anammox) process to treat wastewaters containing antibiotics and heavy metals (such as the liquid fraction of the anaerobically digested swine manure) was studied in this work. The specific anammox activity (SAA) was evaluated by means of manometric batch tests. The effects of oxytetracycline, sulfathiazole, copper and zinc were studied. The experimental data of the short-term assays were fitted with an inhibition model to identify the half maximal inhibitory concentration (IC(50)). After 24 h exposures, IC(50)-values equal to 1.9, 3.9, 650 and 1,100 mg L(-1) were identified for copper, zinc, sulfathiazole and tetracycline respectively. The effect of prolonged exposure (14 days) to oxytetracycline and sulfathiazole was studied by means of repeated batch-assays. Anabolism and catabolism reactions were active during the inhibition tests indicating that anammox bacteria could grow even in the extreme conditions tested. Considering the average concentrations expected in swine wastewaters, the inhibitors studied do not seem to represent a problem for the application of the anammox process. However, in order to verify the effect of these compounds on the growth of anammox bacteria, continuous culture experiments could be conducted.

Microcalorimetric and manometric tests to assess anammox activity.

The present study compares two experimental methods to evaluate Anammox activity based on the assessment of (1) the N(2) production rate by a manometric device, as previously proposed, and (2) the heat production rate by a microcalorimeter. Two samples of Anammox suspended biomass were taken from a pilot-plant, and their specific Anammox activity measured by both techniques. Both methods were successfully applied. As for calorimetric tests, they were performed for the first time on Anammox enriched sludge samples. Comparisons between the specific Anammox activities estimated by manometry and calorimetry and between expected (from the reaction enthalpy) and measured heat productions were performed. Promising results were obtained.

A modified Activated Sludge Model to estimate solids production at low and high solids retention time.

In this paper, a modified version of the IWA-ASM1 model capable of correctly simulating the production of solids over a wide range of solids retention time (SRT) is presented. The parameters of the modified model have been estimated by integrating the results of respirometric and titrimetric tests with those of studies conducted on pilot scale plants that treat industrial wastewaters of differing characteristics. On the basis of the experimental results and their subsequent processing, it appears that the production of solids may be satisfactorily estimated using the modified model in which fractions X(P) and X(I) are supposed to be hydrolysable with a first-order kinetic. In the cases that were examined, the constant of the aforementioned kinetics was estimated to be k(i)=0.012 d(-1) and k(i)=0.014 d(-1), for tannery and textile wastewater respectively. A reliable calibration of the parameter k(i) was possible when data relative to the experiment conducted in the pilot plants for no less than 60 d and in conditions of complete solid retention was utilized.

A simple method to evaluate the short-term biogas yield in anaerobic codigestion of WAS and organic wastes.

The present study was aimed at setting and applying a procedure to measure the anaerobic degradability of different organic substrates by short-term tests (2-7 days) carried out at lab-scale with a low food to biomass (F/M) ratio. All tests were carried out using an acclimated sludge taken from a pilot-plant anaerobic digester (200 L). Trials were performed with a manometric system. The experimental reliability of the device in measuring the anaerobic degradability was assessed by several preliminary tests carried out using acetate and glucose as reference substrates. The average conversion to methane was 99% for acetate and of 83% for glucose. The results of tests in triplicate showed the high repeatability of the method with an average coefficient of variation lower than 2%. Then, the lab-scale procedure was applied to study the short-term anaerobic degradability of complex organic substrates: thickened waste activated sludge, two kinds of organic fraction of municipal solid waste (a kitchen waste and a fruit and vegetable waste collected at the wholesale market of Florence), olive mill wastewater and freshly harvested grass. Results indicated that organic fraction of municipal solid waste, olive mill wastewater and grass were characterized by a much higher anaerobic degradability if compared to the thickened activated sludge, well in agreement with literature data.

An integrated approach in a municipal WWTP: anaerobic codigestion of sludge with organic waste and nutrient removal from supernatant.

Co-digestion appears to be an interesting solution to increase the biogas production of poorly performing under-loaded digesters of waste activated sludge. In the Florence WWTP anaerobic codigestion could increase nitrogen and phosphorus loading rates and thus lower the nutrient removal efficiency. In order to develop an integrated solution to upgrade the Florence WWTP, the different process units were tested in experimental plants. Anaerobic codigestion with source-collected organic solid waste in a pilot-scale bioreactor showed an increase of GPR from 0.15 to 0.45 Nl biogas/l/d with 23% of organic waste loaded. Autotrophic nitrogen removal was carried out in two lab-scale pilot plants which were fed with a real anaerobic supernatant after phosphate removal via struvite formation. The nitritation MBBR has been working for one year at steady-state conditions with a perfect nitrite/ammonium ratio equal to 1:1. Anammox biomass enrichment was performed in a suspended biomass SBR and the specific nitrogen removal rate increased from 1.7 to 58 gN/kgVSS/d in 375 days.

Olive mill wastewater biological treatment by fungi biomass.

Olive oil extraction is one of the most important traditional food industries in the Mediterranean region, especially in Italy. In addition to olive oil, this industry produces by-products, in particular olive mill wastewaters (OMWs) and olive husks, which represent a serious environmental problem. OMWs can be rarely treated in a municipal WWTP, using conventional wastewater treatments. A novel biological process has to be considered in order to treat OMWs. Literature data show that yeasts and different kinds of fungi are able to reduce both the organic and the phenolic content of the OMW. The present work is aimed at investigating the growth of a biomass rich in fungi in a batch reactor filled with OMW and its capacity to degrade the organic and phenolic load. The aerobic OMW degradation obtained using this biomass reached a COD and TP removal efficiency of 86 and 70%, respectively. Respirometric tests have been carried out in order to measure the biomass activity on different substrates: OMW and phenolic compounds (gallic and p-coumaric acids). The polyphenolic biodegradation efficiency of fungi biomass was higher than the one of a non-acclimated activated sludge biomass. Fungi biomass was able to completely degrade pure phenolic compounds.

Oxidative processes for olive mill wastewater treatment.

The present work describes an experimental study carried out in order to investigate the efficiency and feasibility of physical (lime coagulation) and advanced oxidation processes (Ozone and Fenton's process) for olive oil mill wastewater treatment. Particular attention was paid to the degradation of both organic and phenolic compounds. Lime coagulation reaches maximum removal at a pH of 12, with a TP (total polyphenols) and COD reduction of 37 and 26%, respectively. Ozone oxidation is also pH-dependent, showing the higher removal efficiency (91% for TP and 19% for COD) with an initial pH value of 12. Experimental results show a lower efficiency of Fenton's process than ozone in TP removal, reaching a maximum value of 60%. Oxidation trials carried out on gallic and p-coumaric synthetic solutions confirmed ozone and Fenton's efficiency at degrading phenolic compounds. Biological trials, both aerobic and anaerobic, highlighted a significant increase of biodegradability of treated OMW samples if compared to the untreated ones. Respirometric tests showed an increase in BOD of about 20% and anaerobic batch tests provided a methane production up to eight times higher.

MBR pilot plant for textile wastewater treatment and reuse.

An experimental study was carried out in order to evaluate the possibility of upgrading the conventional activated sludge WWTP of Seano (Prato, Italy) which treats municipal and textile wastewaters, by using membrane bioreactor (MBR) technology. The MBR pilot plant, set up within Seano WWTP, was fed with mixed municipal-industrial wastewaters during the first experimental period and with pure industrial wastewaters during the second. Performances and operation of the MBR were evaluated in terms of permeate characteristics and variability (COD, colour, surfactants, total N and P) and other operational parameters (sludge growth and observed yield). According to the experimental results the MBR permeate quality was always superior to the Seano WWTP one and it was suitable for industrial reuse in the textile district of the Prato area. Respirometric tests provided a modified IWA ASM1 model which fits very well the experimental data and can be used for the design and the monitoring of a full-scale MBR pilot plant.

Olive mill wastewater treatment: an experimental study.

Olive oil production, one of the main agro-industries in Mediterranean countries, generates significant amounts of olive mill wastewaters (OMWs), which represent a serious environmental problem, because of their high organic load, the acidic pH and the presence of recalcitrant and toxic substances such as phenolic and lipidic compounds (up to several grams per litre). In Italy, traditional disposal on the soil is the most common way to discharge OMWs. This work is aimed at investigating the efficiency and feasibility of AOPs and biological processes for OMW treatment. Trials have been carried out on wastewaters taken from one of the largest three-phase mills of Italy, located in Quarrata (Tuscany), as well as on synthetic solutions. Ozone and Fenton's reagents applied both on OMWs and on phenolic synthetic solutions guaranteed polyphenol removal efficiency up to 95%. Aerobic biological treatment was performed in a batch reactor filled with raw OMWs (pH = 4.5, T = 30 degrees C) without biomass inoculum. A biomass rich of fungi, developed after about 30 days, was able to biodegrade phenolic compounds reaching a removal efficiency of 70%. Pretreatment of OMWs by means of oxidation increased their biological treatability.

Autotrophic nitrogen removal from anaerobic supernatant of Florence's WWTP digesters.

In municipal WWTP with anaerobic sludge digestion, 10-20% of total nitrogen load comes from the return supernatant produced by the final sludge dewatering. In recent years a completely autotrophic nitrogen removal process based on Anammox biomass has been tested in a few European countries, in order to treat anaerobic supernatant and to increase the COD/N ratio in municipal wastewater. This work reports the experimental results of the SHARON-ANAMMOX process application to anaerobic supernatant taken from the urban Florentine area wastewater treatment plant (S. Colombano WWTP). A nitritation labscale chemostat (7.4 L) has been started-up seeded with the S. Colombano WWTP nitrifying activated sludge. During the experimental period, nitrite oxidising bacteria wash-out was steadily achieved with a retention time ranging from 1 to 1.5 d at 35 degrees C. The Anammox inoculum sludge was taken from a pilot plant at EAWAG (Zurich). Anammox biomass has been enriched at 33 degrees C with anaerobic supernatant diluted with sodium nitrite solution until reaching a maximum specific nitrogen removal rate of 0.065 kgN kg(-1) VSS d(-1), which was 11 times higher than the one found in inoculum sludge (0.005 kgN kg(-1) VSS d(-1). In a lab-scale SBR reactor (4 L), coupled with nitritation bioreactor, specific nitrogen removal rate (doubling time equal to 26 d at 35 degrees C and at nitrite-limiting condition) reached the value of 0.22 kgN kg(-1) VSS d(-1), which was approximately 44 times larger than the rate measured in the inoculum Anammox sludge.

Upgrading of Florence wastewater treatment plant: co-digestion and nitrogen autotrophic removal.

In recent years a completely autotrophic nitrogen removal process based on Anammox biomass has been tested in a few European countries in order to treat anaerobic supernatant and to increase the COD/N ratio in municipal wastewater. This work reports experimental results on a possible technical solution to upgrade the S. Colombano treatment plant which treats wastewater from the Florentine urban area. The idea is to use 50% of the volume of the anaerobic digester in order to treat external sewage sludge (as septic tank sludge) together with waste activated sludge and to treat the resulting effluent on a SHARON-ANAMMOX process in order to remove nitrogen from the anaerobic supernatant. Anaerobic co-digestion, tested in a 200 L pilot plant, enables low cost treatment of septic tank sludge and increases biogas production; however, it also increases the nitrogen load re-circulated to the WWTP, where nitrogen removal efficiency is already low (<50%), due to the low COD/N ratio, which limits predenitrification efficiency. Experimental results from a SHARON process tested in a lab-scale pilot plant show that nitrite oxidising bacteria are washed-out and steady nitrite production can be achieved at retention times in the range 1 - 1.5 days, at 35 degrees C. In a lab-scale SBR reactor, coupled with a nitration bioreactor, maximum specific nitrogen removal rate under nitrite-limiting conditions (with doubling time equal to about 26 days at 35 degrees C) was equal to 0.22 kgN/kgSSV/d, about 44 times the rate measured in inoculum Anammox sludge. Finally, a cost analysis of the proposed upgrade is reported.

Enzymatic synthesis of purine 2'-deoxyriboside and its properties as an inhibitor of adenosine deaminases from calf intestinal mucosa and Bacillus cereus.

Enzymatic synthesis of purine 2'-deoxyriboside was obtained by reacting purine with excess 2-deoxy-alpha-D-ribose-1-phosphate in the presence of commercial bovine nucleoside phosphorylase; the product was isolated by semipreparative reverse phase HPLC with an overall 62% yield. Purine 2'-deoxyriboside was shown to behave as a competitive inhibitor of adenosine deaminase from calf intestinal mucosa and Bacillus cereus, with apparent Ki values of 4.5 and 8.5 microM, respectively.