Understanding the acidification risk of cheese whey anaerobic digestion under psychrophilic and mesophilic conditions.

Anaerobic digestion is a suitable technology to treat cheese whey (CW), a high-strength wastewater from cheesemaking. However, CW anaerobic digestion is limited by its high biodegradability, acidic pH, and lack of alkalinity. This publication evaluated the acidification risk of CW anaerobic digestion under psychrophilic and mesophilic conditions, aiming to improve digester design, operation, and decision-making when facing instability periods. To evaluate the acidification risk of CW anaerobic digestion, biochemical methane potential (BMP) tests were carried out at four different organic loads, each under psychrophilic (20 °C) and mesophilic (35 °C) conditions. Besides methane production, pH, soluble chemical oxygen demand, volatile fatty acid and alcohols were also monitored. Experimental results showed that CW can be successfully degraded under both temperature conditions, with methane yields of 389-436 mLCH4/gVS. The organic load had a greater impact on the accumulation of intermediate products than temperature, indicating that process inhibition by overloading is plausible under psychrophilic and mesophilic conditions. However, the degradation rate under mesophilic conditions was faster than under psychrophilic conditions. Experimental results also revealed a higher imbalance between fermentation and methanogenesis rate under psychrophilic conditions, which resulted in higher concentrations of intermediate products (volatile fatty acids and alcohols) and prolonged lower pHs. These results indicate that the degradation of intermediate products is less favourable under psychrophilic conditions compared to mesophilic conditions. This implies that psychrophilic digesters have a lower capacity to recover from process disturbances, increasing the risk of process underperformance or even failure under psychrophilic conditions.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) in human breast milk from Colombia: A probabilistic risk assessment approach.

Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) are ubiquitous environmental contaminants. They were produced in relatively large volumes in the last century and are now subject to long-term monitoring and regulated under the United Nations Stockholm Convention (SC) on persistent organic pollutants (POPs). Though restricted, human exposure is still a concern and in some regions of the globe the information on the health risk is limited. Sixty breast milk samples from nursing mothers were collected between 2014 and 2015, residing in Bogota, Cartagena, and Medellin, which are industrialized cities in Colombia. This is the first comprehensive study to determine the concentrations in breast milk of PBDEs (n = 7), PCBs (n = 29), and OCPs (n = 28) in Colombia. The detection frequency of POPs, including BDE-47, CB-138, CB-153, CB-156, and CB-180, as well as several OCPs such as chloroneb, aldrins, HCHs, DDTs, and heptachlor, was found to be 100% in all samples tested. The mean concentrations of the analyzed legacy POPs were ∑3DDTs (423 ng/g lw) > chloroneb (50.1 ng/g lw) > ∑2permetrins (17.5 ng/g lw) > ∑2aldrins (16.7 ng/g lw) > 29 PCBs (15.04 ng/g lw) > ∑2chlordanes (CHLs) (11.2 ng/g lw) ≈ ∑3endosulfans (11.1 ng/g lw) > ∑2heptachlors (2.43 ng/g lw) > 7PBDEs (2.1 ng/g lw) > ∑4HCHs (0.58 ng/g lw). The results of this study suggest that the concentrations of DDTs were present in breast milk samples from Colombia at levels comparable to those found in previous studies conducted in other countries such as Brazil, Uruguay, Chile, and various Asian countries. The concentrations of PBDE and PCB congeners, as well as many pesticides, were found to be significantly correlated with each other. This suggests that these substances may have similar sources of exposure. The strength of the pair correlation among concentrations of POPs was assessed using Spearman's correlation coefficients, which varied from r = 0.62 for the association between BDE-47 and CB-153, to a high correlation of 0.99 for the correlation between γ-Chlordane and heptachlor. This suggests that these POPs may share similar sources, such as diet. An exposure assessment model obtained by Monte Carlo simulation showed that infants were exposed to low concentrations of POPs with exception of p,p'-DDE and Aldrin, in which 25th, 50th and 95th percentiles were greater than the threshold reference values of non-carcinogenic effects suggested by US-EPA regulations while the 90th percentile of pg TEQ/Kg-bw/day for dl-PCBs was above of the tolerable daily intake (TDI) proposed by the World Health Organization (WHO). Therefore, the health risk of infants exposed to OCPs and dl-PCBs should be exanimated continually through biomonitoring programs in the Colombian population.

Life cycle inventory data for ethyl levulinate production from Colombian rice straw.

This data article is associated with the research article "Sustainable production of ethyl levulinate by levulinic acid esterification obtained from Colombian rice straw". This paper shows the methodology to calculate the Life Cycle Inventory (LCI) of the foreground system to perform the Life Cycle Assessment (LCA) of the ethyl levulinate (EL) production from Colombian rice straw (RS). This process encompasses two main stages: (i) RS production (involving cultivation and harvesting) and (ii) EL production (involving acid hydrolysis, levulinic acid (LA) purification, and El production). On one hand, foreground data related to paddy rice cultivation was gathered from the literature review. Besides, emissions of the cultivation stage were calculated using the IPCC (Intergovernmental Panel on Climate Change) methodology. The SQCB (Sustainable Quick Check for Biofuels) methodology was used to calculate NH3, NOx, N2O and NO3 emissions, whereas the SALCA (Swiss Agricultural Life Cycle Assessment) model was used to calculate phosphorous emissions to water. The Turc method was employed to calculate the irrigation requirements based on the rainfall and agrological features of rice culture. On the other hand, foreground data related to RS conversion to EL within a biorefinery scheme was obtained from simulation using Aspen Plus v.12. Lastly, background data associated with raw materials, catalysts, and utilities were gathered from Ecoinvent database. All the inventories are meaningful to carry out future environmental assessments involving sustainable production processes using RS as raw material or biorefinery processes using dilute acid hydrolysis.

Integration of steam gasification and catalytic reforming of lignocellulosic biomass as a strategy to improve syngas quality and pollutants removal.

Residual biomass gasification is a promising route for the production of H2-rich syngas. However, the simultaneous formation of pollutants such as light hydrocarbons (HCs), benzene, toluene and xylenes (BTEX), polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) during gasification must be controlled. As a result, this study evaluated the effect of temperature and catalytic reforming over a Rh-Pt/CeO2-SiO2 catalyst during steam gasification of sugarcane residual biomass on syngas composition and pollutant removal. The above was carried out in a horizontal moving reactor, an Amberlite XAD-2 polyaromatic resin was used to collect the contaminants and characterization of the catalyst was performed. In this study, a concentration of up to 37 mol% of H2, a yield of 23.1 g H2 kg-1biomass, and a H2/CO ratio ≥2 were achieved when gasification and reforming were integrated. In addition, the catalyst characterization showed that Rh-Pt/CeO2-SiO2 was not susceptible to sintering and favored the formation of hydroxyl groups that promoted CO oxidation, thereby increasing the H2/CO ratio, as confirmed by in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). At 800 °C, where a high H2 yield was obtained, 209 g Nm-3 of light HCs and BTEX, 10.9 g Nm-3 of PAHs, and 32.5 ng WHO-TEQ Nm-3 of PCDD/Fs were formed after gasification. Interestingly, after catalytic reforming, 62% of light HCs and BTEX, 60% of PAHs, and 94% of PCDD/Fs were removed, leading to cleaner syngas with properties that allow it to be used in a wide range of energy applications.

Polycyclic aromatic hydrocarbons (PAHs) in human breast milk from Colombia: Spatial occurrence, sources and probabilistic risk assessment.

The diet is the main route that polycyclic aromatic hydrocarbons (PAHs) enter the body and measuring breast milk is one of the best ways to understand the maternal body burden and can be passed on to infants. In this study, it was determinate the concentrations of 23 PAHs in 60 milk samples taken from 3 cities in Colombia and to determine the potential routes of exposure and risk to human health. On average, concentration for the ∑PAHs across all locations was 186.6 ng g-1, lipid mass (LM), with city means of 260.1, 175.7, and 123.9 ng g-1 LM for Cartagena, Bogota and Medellin, respectively. Monte Carlo simulations were used to estimate the hazard quotient (HQ) and incremental lifetime cancer risk (ILCR) for infant dietary exposure to PAHs. HQs were below the safe thresholds (HQ = 1) while ILCRs were greater than the reference value equal to 10-6 (mg kg-1day-1). Dietary source assessment indicated that fish is a significant source of PAHs, with mothers that consumed fish at least once per week having ∼2.5 times greater PAH milk concentrations than other groups. While a disparity was also observed among consumers of exclusively marine (∑PAHs 198.5 ng g-1 LM) or freshwater fish (∑PAHs 85.7 ng g-1 LM). However, geographical considerations can be significant in this finding.

Life cycle inventory data for power production from sugarcane press-mud.

This data article is associated with the research article "Technical and environmental analysis on the power production from residual biomass using hydrogen as energy vector". This paper shows the procedure to calculate the Life Cycle Inventory (LCI) of the foreground system to perform the Life Cycle Assessment (LCA) of the power production from sugarcane press-mud. Said process encompasses four main stages: i) bioethanol production; ii) bioethanol purification; iii) syngas production and purification; and iv) power production. Additionally, other processes such as biomethane production and manufacturing of catalyst were included. Foreground data related to bioethanol production was gathered from experimental procedures at lab-scale. While foreground data, concerning the other processes such as bioethanol purification, syngas production and purification, power production, and biomethane production, was built by using material and energy flows obtained from Aspen Plus®. Lastly, LCI of the catalyst manufacturing was built based on literature review and the approach stated by Ecoinvent. All the inventories are meaningful to carry out future environmental assessments involving sustainable energy systems based on bioethanol, biomethane, or hydrogen.

Proposal of an open-source computational toolbox for solving PDEs in the context of chemical reaction engineering using FEniCS and complementary components.

In this contribution, an open-source computational toolbox composed of FEniCS and complementary packages is introduced to the chemical and process engineering field by addressing two case studies. First, the oxidation of o-xylene to phthalic anhydride is modelled and used as a FEniCS' proof-of-concept based on a comparison with the software Aspen Custom Modeler (ACM). The results show a maximum absolute error of 2% and thus a good FEniCS/ACM agreement. Second, synthetic natural gas (SNG) production through CO2 methanation is covered in further detail. In this instance, a parametric study is performed for a tube bundle fixed-bed reactor employing a two-dimensional and transient pseudo-homogeneous model. An operating window for critical variables is evaluated, discussed, and successfully contrasted with the literature. Therefore, the computational toolbox methodology and the consistency of the results are validated, strengthening FEniCS and complements as an interesting alternative to solve mathematical models concerning chemical reaction engineering.

Controlling sugarcane press-mud fermentation to increase bioethanol steam reforming for hydrogen production.

Hydrogen (H2) production from sugarcane press-mud, a waste obtained from the non-centrifugal sugarcane agroindustry, was assessed by coupling hydrolysis, fermentation, purification, and ethanol steam reforming (ESR). Two culture media were employed on three different sugarcane press-mud samples to produce bioethanol by fermentation using Saccharomyces cerevisiae at 30 °C. One culture medium was supplemented with nutrients and the other without supplementation. The supplementation did not have a significant effect over ethanol production (∼82.1 g L-1) after 70 h fermentation, but the concentration of the impurities was always lower under supplemented conditions. Among tested impurities, differences in 3-methyl-1-butanol showed the effect of the supplementation on the ESR over RhPt/CeO2-SiO2 catalyst at 700 °C, where the H2 yield decreased significantly in the presence of 3-methyl-1-butanol (p < 0.05). The spearman correlation coefficient showed that the H2 yield was correlated with the 3-methy-1-butanol content (RHO = -0.929) and carbon deposits (RHO = -0.964). Therefore, supplemented bioethanol could deliver 3.0 g H2 kg-1 sugarcane press-mud, which is almost twice that of the non-supplemented samples, likely due to the reduction of harmful impurities in the bioethanol. Additionally, supplemented conditions allowed for energy savings in the process and improved catalyst stability. This study provides insights into the effect of supplementing culture media to produce purer bioethanol samples, which further deliver higher H2 yields by ESR.

Effect of the incorporation of chitosan on the physico-chemical, mechanical properties and biological activity on a mixture of polycaprolactone and polyurethanes obtained from castor oil.

In the present study, polyurethane materials were obtained from castor oil, polycaprolactone and isophorone diisocyanate by incorporating different concentrations of chitosan (0.5, 1.0 and 2.0% w/w) as an additive to improve the mechanical properties and the biological activity of polyurethanes. The polyurethanes were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, stress/strain fracture tests and swelling analysis, and the hydrophilic character of the surface was determined by contact angle trials. The objectives of the study were to evaluate the effect of the incorporation of chitosan on the changes of the physico-chemical and mechanical properties and the in vitro biological activity of the polyurethanes. It was found that the incorporation of chitosan enhances the ultimate tensile strength of the polyurethanes and does not affect the strain at fracture in polyurethanes with 5% w/w of polycaprolactone and concentrations of chitosan ranging from 0 to 2% w/w. In addition, PCL5-Q-PU formulations and their degradation products did not affect cell viability of L929 mouse fibroblast and 3T3, respectively. Polyurethane formulations showed antibacterial activities against Staphylococcus aureus and Escherichia coli bacteria. The results of this study have highlighted the potential biomedical application of this polyurethanes related to soft and cardiovascular tissues.

Microbial degradation, cytotoxicity and antibacterial activity of polyurethanes based on modified castor oil and polycaprolactone.

The objective of this study was to assess the effects of type of polyol and concentration of polycaprolactone (PCL) in polyurethanes (PUs) on microbial degradability, cytotoxicity, biological properties and antibacterial activity to establish whether these materials may have biomedical applications. Chemically modified and unmodified castor oil, PCL and isophorone diisocyanate in a 1:1 ratio of NCO/OH were used. PUs were characterized by stress/strain fracture tests and hardness (ASTM D 676-59). Hydrophilic character was determined by contact angle trials and morphology was evaluated by scanning electron microscopy. Degradability with Escherichia coli and Pseudomonas aeruginosa was evaluated by measuring variations in the weight of the polymers. Cytotoxicity was evaluated using the ISO 10993-5 (MTT) method with mouse embryonic fibroblasts L-929 (ATCC® CCL-1) in direct contact with the PUs and with NIH/3T3 cells (ATCC® CRL-1658) in indirect contact with the PUs. Antimicrobial activity against E. coli and P. aeruginosa was determined. PUs derived from castor oil modified (P0 and P1) have higher mechanical properties than PUs obtained from castor oil unmodified (CO). The viability of L-929 mouse fibroblasts in contact with polymers was greater than 70%. An assessment of NIH/3T3 cells in indirect contact with PUs revealed no-toxic degradation products. Finally, the antibacterial effect of the PUs decreased by 77% for E. coli and 56% for P. aeruginosa after 24 h. These results indicate that PUs synthesized with PCL have biocidal activity against Gram-negative bacteria and do not induce cytotoxic responses, indicating the potential use of these materials in the biomedical field.

Catalytic hydrodechlorination of trichloroethylene in a novel NaOH/2-propanol/methanol/water system on ceria-supported Pd and Rh catalysts.

The catalytic hydrodechlorination (HDC) of high concentrations of trichloroethylene (TCE) (4.9 mol%, 11.6 vol%) was studied over 1%Pd, 1%Rh and 0.5%Pd-0.5%Rh catalysts supported on CeO2 under conditions of room temperature and pressure. For this, a one-phase system of NaOH/2-propanol/methanol/water was designed with molar percentages of 13.2/17.5/36.9/27.6, respectively. In this system, the alcohols delivered the hydrogen required for the reaction through in-situ dehydrogenation reactions. PdRh/CeO2 was the most active catalyst for the degradation of TCE among the evaluated materials, degrading 85% of the trichloroethylene, with alcohol dehydrogenation rates of 89% for 2-propanol and 83% for methanol after 1 h of reaction. Fresh and used catalysts were characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric analysis (TGA). These results showed important differences of the active phase in each catalyst sample. Rh/CeO2 had particle sizes smaller than 1 nm and the active metal was partially oxidized (Rh(0)/Rh(+δ) ratio of 0.43). This configuration showed to be suitable for alcohols dehydrogenation. On the contrary, Pd/CeO2 showed a Pd completed oxidized and with a mean particle size of 1.7 nm, which seemed to be unfavorable for both, alcohols dehydrogenation and TCE HDC. On PdRh/CeO2, active metals presented a mean particle size of 2.7 nm and more reduced metallic species, with ratios of Rh(0)/Rh(+δ) = 0.67 and Pd(0)/Pd(+δ) = 0.28, which showed to be suitable features for the TCE HDC. On the other hand, TGA results suggested some deposition of NaCl residues over the catalyst surfaces. Thus, the new reaction system using PdRh/CeO2 allowed for the degradation of high concentrations of the chlorinated compound by using in situ hydrogen liquid donors in a reaction at room temperature and pressure.

Characterization of fly ash from a hazardous waste incinerator in Medellin, Colombia.

Bag filter (BF) fly ash from a hazardous waste incinerator located in Medellín, Colombia was characterized. Particle size distribution, chemical composition, metal loading, surface area, morphology, and chemical environment were assessed before and after fly ash extraction with toluene. Fly ash consists of low surface area platelets of SiO(2) smaller than 0.5 microm agglomerated in spheres between 20 and 100 microm. High concentration of sodium chloride, carbon, and heavy metals such as Cu, Fe, Pb, Hg, Cd, Co and Mn are deposited over the fly ash surface. The carbon is oxidized and forms different structures such as amorphous carbon black, nano balls and more crystalline fullerenes like nano onions. The high concentration of dioxins, furans and dioxin-like PCBs (superior to 185 ng WHO-TEQ/g) is favored by oxidized carbon, chlorine and metals such as Cu and Fe on the shell of the particles. Before and after toluene extraction, fly ash samples presented similar morphology. However, after extraction their particle size increased while their surface area decreased by 35% and the carbon and metal contents decreased by 35% and 50%, respectively.

The effect of NaOH on the liquid-phase hydrodechlorination of dioxins over Pd/gamma-Al2O3.

The effect of sodium hydroxide on the-liquid phase hydrodechlorination (LPHDC) of polychlorinated dibenzo- p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) over 2% Pd/gamma-Al 2O 3 was evaluated. Reactions were carried out using 2-propanol both as a hydrogen donor and as a solvent. Fresh and used catalyst samples were characterized by BET, hydrogen chemisorption, TEM/EDS, XPS, and TPR. When the reaction mixture contained no NaOH, active-phase leaching and Pd-C formation were observed even after 10 min of reaction. Therefore, sodium hydroxide appears to be required to maintain surface metal clusters on the support and avoid binding of carbon species to the active metal. On the other hand, excess NaOH in the reaction mixture led to deposition of organic and inorganic solid residues on the catalyst surface, blocking the active sites. Under the conditions of this study, the addition of 30 mg of NaOH maintained the basicity of the system and diminished deposition of solid residues on the catalyst samples, and almost 100% detoxification was reached after a 3 h reaction.