Aerobic digestibility of waste aerobic granular sludge (AGS) assessed by respirometry, physical-chemical analyses, modeling and 16S rRNA gene sequencing.

Research has evolved on aerobic granular sludge (AGS) process, but still there are very few studies on the treatment of excess AGS sludge, with almost none considering its aerobic digestion. Here therefore, the aerobic digestibility of typical AGS sludge was assessed. Granules were produced from acetate-based synthetic wastewater (WW) and were subjected to aerobic digestion for 64 d. The stabilization process was monitored over time through physical-chemical parameters, oxygen uptake rates (OUR) and 16S rRNA gene sequencing. The microbial analyses revealed that the cultivated granules were dominated by slow-growing bacteria, mainly ordinary heterotrophic organisms with potential for polyhydroxyalkanoates (PHA) aerobic storage (PHA-OHOs), polyphosphate and glycogen accumulating organisms (PAOs and GAOs), fermentative anaerobes and nitrifiers (AOB and NOB). Differential abundance analysis of the bacterial data (before versus after digestion) discriminated between the most vulnerable microbiome genera and those most resistant to aerobic digestion. Furthermore, modeling of the stabilization process determined that the endogenous decay rate constant (bH) for the heterotrophs present in the granules was notably low; bH = 0.05 d-1 (average), four times less than for common activated sludge (AS), which is rated at 0.2 d-1. For first time, the research reveals another important feature of AGS sludge, i.e. the slow-decaying character of its bacteria (along with their known slow-growing character). This results in slower stabilization, need of bigger digesters and reconsideration of the specific OUR limits in biosolids regulations (SOUR limit of 1.5 mg/gTSS.h), for waste AGS compared to conventional waste AS. The study suggests that aerobic digestion of waste AGS (fully-granulated) could differ from that of conventional AS. Future work is needed on aerobic digestibility of real AGS sludges from municipal and industrial WWs, compared to synthetic WWs.

Ordinary heterotrophic organisms with aerobic storage capacity provide stable aerobic granular sludge for C and N removal.

The study investigated the mechanisms and microbial communities underlying the long-term stability and removal performances shown by aerobic granular sludge (AGS) reactor involving polyhydroxyalkanoates (PHA) aerobic-storing bacteria. The characteristics of the sludge, removal performances and bacterial community structure were determined. The prevailing metabolic phenotype was similar in the parent conventional activated sludge (CAS) reactor and its upgraded AGS version, showing high COD and NH4 uptake, versus low P and N reduction. Polyphosphate and glycogen accumulating organisms, PAO and GAO, were not enriched in the reactors despite initial targeting of anaerobic-aerobic cycle. Instead, PHA-aerobic storing bacteria (Thauera and Paracoccus) were dominant, but revealing a stable AGS system for BOD and N removal. The PAO/GAO failed selection and Thauera overgrowth were analyzed for beneficial use in developing alternative AGS technology for BOD and N removal applications.

Microbial mortality behavior promoted by silver (Ag+/Ago)-modified zeolite-rich tuffs for water disinfection.

BACKGROUND: In developing countries, death due to diseases caused by fecal-oral ingestion can be avoided by taking action on drinking water issues. Adequate access to water treatment systems to reduce infections is a critical cause. Silver has been used as an antibacterial product, including biomedical applications. Therefore, in this paper, the effect of the chemical speciation of silver from silver-modified zeolite-rich tuffs on the mortality of Escherichia coli (E. coli), Streptococcus faecalis (S. faecalis) and Candida albicans (C. albicans) suspended in aqueous solution was investigated for disinfection purposes. METHODS: The following aspects were considered to develop the investigation: a) the technique to prepare the modified zeolitic materials, either with ionic silver or silver nanoparticles, which were obtained in two ways: one, with grapefruit extract and the second, by using non-thermal plasma generated in a dielectric barrier discharge reactor of parallel plates; b) the response of the prokaryotes (bacteria) and eukaryote (yeast) microorganisms to disinfectant agents in batch systems; c) the disinfection processes as a function of time to obtain kinetics parameters; and d) the kinetics of the silver release from the silver-modified zeolite-rich tuffs, considering the models of Higuchi and Korsmeyer. The zeolitic materials were characterized by low-vacuum scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). RESULTS: The non-thermal plasma reduced ionic silver is more efficient at generating silver compounds with several oxidation states, which are essential during the microbial inhibition process. For the bacterial (E. coli and S. faecalis), the materials with nanoparticles were efficient to inactivate them. However, the yeast (C. albicans) reaches the total inactivation when the zeolitic material contains ionic silver in the crystalline network. CONCLUSION: The E. coli, S. faecalis and C. albicans survival behavior suspended in aqueous solutions after contact with Ag-modified natural zeolites depends on the chemical speciation of the silver present in these materials, Ag+1 in the case of OAgiZ or nanoparticles of Ago promoted by the grapefruit extract (OAgnpTZ), as well as by non-thermal plasma generated in a dielectric barrier discharge reactor of parallel plates (OAgnpPZ). In general, the concentration of silver in the aqueous solution after the disinfection process cannot exceed the recommended levels established for international organizations. The OAgnpPZ is a potential microbicide agent against E. coli and C. albicans, and the OAgn pTZ for F. faecalis.Graphical abstractARTWORK.

Fixed-bed column system for Cd2+ uptake from aqueous solution by sodium- and thiourea-modified clinoptilolite-rich tuff.

Two kinds of clinoptilolite-rich tuffs from the state of Sonora (Mexico), previously treated with NaCl solution and then modified with thiourea, were investigated to remove Cd2+ from aqueous solution in a fixed-bed column system. Experiments were conducted with a 30 mg L-1 Cd2+ solution at a pH value of 5 and three-bed heights of sodium- and thiourea-modified clinoptilolite-rich tuffs. The experimental data were examined with the bed depth service time model (BDST), the Thomas model, and a mass balance approach. According to the BDST model, the dynamic sorption capacity (No) for the thiourea-modified clinoptilolite-rich tuff was 0.0357 Kg L-1. This value corresponded to 1.2 times higher than that for sodium-modified clinoptilolite-rich tuff (0.0287 Kg L-1). The experimental data obtained for sodium- modified clinoptilolite-rich tuff (ZSGNa) with 3 cm of bed height, fitted to the Thomas model, with R2 = 0.9679 and Cd sorption capacity of 35.4 mg g-1, while for the thiourea-modified clinoptilolite-rich tuff (ZSGThio) with 4.5 cm of bed height, was 36.52 mg g-1 with R2 = 0.9368. The parameters calculated with the mass balance model describe a favourable process where the system with ZSGThio (6 cm bed height) had the best performance for sorption capacity up to the breakthrough point, qb = 22.35 mg g-1. The zeolite modified with thiourea exhibited higher capacity in Cd2+ removal than the one modified with NaCl, in the column with 6 cm of bed height. To investigate the mechanisms of removal of Cd2+ by the modified zeolites, Na⁺ was measured to determine the milliequivalents of cadmium removed.

Removal of Co by carbonaceous material obtained through solution combustion of tamarind shell.

New carbonaceous materials were obtained through solution combustion process of tamarind shell in the presence of urea and ammonium nitrate, and all of them were tested for Co removal. The effect of temperature (from 600 to 1000°C) and water volume on surface texture of carbonaceous material and its adsorptive capacity was evaluated. Scanning electron microscope, Fourier transform infrared spectroscopy, X-ray powder diffraction, and Brunauer-Emmett-Teller (BET) model were used to characterize the obtained carbonaceous material before applying for the removal of cobalt. The point of zero charge was also determined. The results indicate that BET-specific surface areas ranged from 6.40 to 216.72 m2g-1 for the carbonaceous materials obtained at 600, 700, 800, 900, and 1000°C. The one obtained at 900°C (CombTSF900) was found to be the most effective adsorbent for the removal of Co(II) ions from aqueous solutions, with a maximum sorption capacity (Qmax) of 43.56 mg/g. Carbonaceous material obtained through the solution combustion process improves morphological characteristics of adsorbent in a short time, and could be used as an alternative method for the removal of cobalt.

Comparison between silver- and copper-modified zeolite-rich tuffs as microbicide agents for Escherichia coli and Candida albicans.

Zeolite-rich tuff from the State of Chihuahua was modified with silver or copper ions (ZChAg and ZChCu) to evaluate its microbicidal effect against Escherichia coli (E. coli) and Candida albicans (C. albicans) suspended in an aqueous solution in order to compare the microbial disinfection kinetics between bacteria and yeast. The zeolite-rich tuff was treated with AgNO3 or CuCl2 solutions. The materials obtained were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and the textural properties were also determined by BET-analyses. The concentration of Ag and Cu was verified in the zeolitic materials using neutron activation analysis. The experimental data were adjusted to both Chick and Chik-Watson models to describe the kinetic behavior of the process. It was found that when the mass of ZChAg increased, the survival microorganisms notably decreased. The E. coli and C. albicans showed higher resistance in contact with ZChCu even when the mass of such material was 10-20 times higher than the mass of ZChAg. Chick and Chik-Watson constants showed that the kinetics of the disinfection process depended on the desorption of the exchange ion that modified the structure of the zeolitic material, its concentration in aqueous medium, its oligodynamic properties, and each microorganism's characteristics (Gram-negative bacteria and yeast). The kinetic desorption of Ag and Cu from the corresponding modified-zeolite-rich tuffs was also considered in this work. In this case, the Higuchi and Korsmeyer-Peppas models were applied.

Activated sludge mass reduction and biodegradability of the endogenous residues by digestion under different aerobic to anaerobic conditions: Comparison and modeling.

This study was performed to identify suitable conditions for the in-situ reduction of excess sludge production by intercalated digesters in recycle-activated sludge (RAS) flow. The objective was to compare and model biological sludge mass reduction and the biodegradation of endogenous residues (XP) by digestion under hypoxic, aerobic, anaerobic, and five intermittent-aeration conditions. A mathematical model based on the heterotrophic endogenous decay constant (bH) and including the biodegradation of XP was used to fit the long-term data from the digesters to identify and estimate the parameters. Both the bH constant (0.02-0.05 d(-1)) and the endogenous residue biodegradation constant (bP, 0.001-0.004 d(-1)) were determined across the different mediums. The digesters with intermittent aeration cycles of 12 h-12 h and 5 min-3 h (ON/OFF) were the fastest, compared to the aerobic reactor. The study provides a basis for rating RAS-digester volumes to avoid the accumulation of XP in aeration tanks.

Carbonaceous material obtained from exhausted coffee by an aqueous solution combustion process and used for cobalt (II) and cadmium (II) sorption.

New carbonaceous materials were obtained using a fast aqueous solution combustion process from mixtures of exhausted coffee, ammonium nitrate (oxidizer) and urea (fuel) heated at 600, 700, 800 or 900 °C. The resulting powders were effective adsorbents for removing Co(II) and Cd(II) from aqueous solutions. Exhausted coffee was also calcined at different temperatures and compared. The products were characterized, and the obtained carbons had BET specific surface areas of 114.27-390.85 m(2)/g and pore diameters of 4.19 to 2.44 nm when the temperature was increased from 600 to 800 °C. Cobalt and cadmium adsorption by the carbonaceous materials was correlated with the maximum adsorption capacities and specific surface areas of the materials. The method reported here is advantageous because it only required 5 min of reaction to improve the textural properties of carbon obtained from exhausted coffee, which play an important role in the material's cobalt and cadmium adsorption capacities.

Aerobic stabilization of biological sludge characterized by an extremely low decay rate: modeling, identifiability analysis and parameter estimation.

Aerobic digestion batch tests were run on a sludge model that contained only two fractions, the heterotrophic biomass (XH) and its endogenous residue (XP). The objective was to describe the stabilization of the sludge and estimate the endogenous decay parameters. Modeling was performed with Aquasim, based on long-term data of volatile suspended solids and chemical oxygen demand (VSS, COD). Sensitivity analyses were carried out to determine the conditions for unique identifiability of the parameters. Importantly, it was found that the COD/VSS ratio of the endogenous residues (1.06) was significantly lower than for the active biomass fraction (1.48). The decay rate constant of the studied sludge (low bH, 0.025 d(-1)) was one-tenth that usually observed (0.2d(-1)), which has two main practical significances. Digestion time required is much more long; also the oxygen uptake rate might be <1.5 mg O2/gTSSh (biosolids standards), without there being significant decline in the biomass.

As(III) and As(V) sorption on iron-modified non-pyrolyzed and pyrolyzed biomass from Petroselinum crispum (parsley).

The sorption of As(III) and As(V) from aqueous solutions onto iron-modified Petroselinum crispum (PCFe) and iron-modified carbonaceous material from the pyrolysis of P. crispum (PCTTFe) was investigated. The modified sorbents were characterized with scanning electron microscopy. The sorbent elemental composition was determined with energy-dispersive X-ray spectroscopy (EDS). The principal functional groups from the sorbents were determined with FT-IR. The specific surfaces and points of zero charge (pzc) of the materials were also determined. As(III) and As(V) sorption onto the modified sorbents were performed in a batch system. After the sorption process, the As content in the liquid and solid phases was determined with atomic absorption and neutron activation analyses, respectively. After the arsenic sorption processes, the desorption of Fe from PCFe and PCTTFe was verified with atomic absorption spectrometry. The morphology of PC changed after iron modification. The specific area and pzc differed significantly between the iron-modified non-pyrolyzed and pyrolyzed P. crispum. The kinetics of the arsenite and arsenate sorption processes were described with a pseudo-second-order model. The Langmuir-Freundlich model provided the isotherms with the best fit. Less than 0.02% of the Fe was desorbed from the PCFe and PCTTFe after the As(III) and As(V) sorption processes.

Synthesis, characterization and adsorptive properties of carbon with iron nanoparticles and iron carbide for the removal of As(V) from water.

This manuscript presents the synthesis of carbon modified with iron nanoparticles (CFe) and iron carbide (CarFe) from the pyrolyzed crown leaves of pineapple (Ananas comosus) treated with iron salts. The materials that were obtained were used for the removal of As(V) from aqueous media. The carbonaceous materials were characterized by Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS) and Mossbauer Spectroscopy. The specific area (BET), number site density and point of zero charge (pH(pzc)) were also determined. The kinetic parameters were obtained by fitting the experimental data to the pseudo-first-order and pseudo-second-order models. Different isotherm models were applied to describe the As(V) adsorption behavior. The kinetics of As(V) sorption by CFe and CarFe was well defined for the pseudo-second-order model (R(2) = 0.9994 and 0.999, respectively). The maximum As(V) uptake was 1.8 mg g(-1) for CFe and 1.4 mg g(-1) for CarFe. The results obtained indicated that both materials are equally useful for As(V) sorption. The As(V) experimental isotherm data were described by the Freundlich model for CFe and CarFe.

Silicalite-1, an adsorbent for 2-, 3-, and 4-chlorophenols.

The adsorption of the three chlorophenol isomers, ortho, meta and para, by silicalite-1 has been studied at 30 °C, below the solubility (at the same temperature) in water. Large differences, up to 30 times, have been observed between the adsorption of the para- vs. the ortho-isomer. The difference of behavior observed between the isomers is assigned to the tendency to self-organization of the para-isomer. It seems probable that the adsorption sites are at the intersection channels. From a technical point of view, silicalite-1 seems a competitive adsorbent for p-chlorophenol.

Initial-rate based method for estimating the maximum heterotrophic growth rate parameter (µHmax).

Currently, the method most used for measuring the maximum specific growth rate (µ(Hmax)) of heterotrophic biomass is by respirometry, using growth batch tests performed at high food/microorganism ratio. No other technique has been suggested, although the former approach was criticized for providing kinetic constants that could be unrepresentative of the original biomass. An alternative method (seed-increments) is proposed, which relies on measuring the initial rates of respiration (r(O2)(_ini)) at different seeding levels, in a single batch, and in the presence of excess readily biodegradable substrate (S(S)). The ASM1-based underlying equations were developed, which showed that µ(Hmax) could be estimated through the slope of the linear function of r(O2)(_ini)·(V(WW)+v(ML)) vs v(ML) (volume of mixed liquor inoculum); V(WW) represent the wastewater volume added. The procedure was tested, being easy to apply; the postulated linearity was constantly observed and the method is claimed to measure the characteristics of the biomass of interest.

Effect of the pH and temperature on the biosorption of lead(II) and cadmium(II) by sodium-modified stalk sponge of Zea mays.

OBJECTIVE: The present work was carried out to investigate the effects of temperature, initial pH, initial concentration, and contact time on the biosorption of lead (Pb) and cadmium (Cd) by modified stalk sponge of Zea mays using a batch technique. METHODS: The biomass was chemically modified with a 0.1 M NaCl solution. The lead and cadmium sorption process was evaluated at 20°C, 30°C, 40°C, and 50°C. RESULTS: The results showed that the modified stalk sponge of Z. mays had a good capacity for biosorption of Pb(II) and Cd(II). The kinetic behavior was described by the pseudo-second-order model for both metallic species. The experimental isotherms obtained at different temperatures were fit with Langmuir and Freundlich models. Thermodynamic parameters ΔH(0) and ΔS(0) were calculated using the van't Hoff equation, and the results show that Pb(II) and Cd(II) sorption by modified stalk sponge of Z. mays is an exothermic and spontaneous process.

Phenol sorption on surfactant-modified Mexican zeolitic-rich tuff in batch and continuous systems.

Surfactant modified clinoptilolite-rich tuff was used for the removal of phenol from aqueous solutions. The zeolitic rock from Oaxaca (Mexico) was treated with sodium chloride and then modified with hexadecyltrimethylammonium chloride or bencylcetildimethylammonium chloride in different experimental conditions. Phenol sorption isotherms and column experiments were performed; in both cases, phenol was determined in the aqueous solutions by UV-vis spectroscopy. The results showed that the sorption of phenol depends on the quantities of surfactant in the zeolitic rocks, the kind of surfactant, modification conditions and pH of the solutions. When the initial concentration of phenol increased, the adsorption of phenol in the surfactant-modified zeolite increased and the experimental data was best adjusted to the Langmuir model. The saturation of the columns rapidly reached high percentages.

Adsorption kinetic of arsenates as water pollutant on iron, manganese and iron-manganese-modified clinoptilolite-rich tuffs.

Arsenate adsorption from aqueous solutions onto clinoptilolite-heulandite rich tuffs modified with iron or manganese or a mixture of both iron and manganese in this work was investigated. A kinetic model was considered to describe the arsenates adsorption on each zeolitic material. The modified clinoptilolite-heulandite rich tuffs were characterized by scanning electron microscopy and X-ray diffraction analysis. The elemental composition and the specific surface area of the zeolitic material were also determined. The arsenate adsorption by the modified zeolites was carried on in a batch system considering a contact time from 5 min to 24h for the kinetic experimentation. The arsenic was detected by atomic absorption spectrometer using a hydride generator. The kinetics of the arsenate adsorption processes were described by the pseudo-second-order model and the obtained parameter k varies from 0.15 to 5.66 microg/gh. In general, the results suggested that the kinetic adsorption of arsenates on the modified clinoptilolite-rich tuffs depend of the metallic specie that modified the surface characteristics of the zeolitic material, the chemical nature of the metal as well as the association between different metallic chemical species in the zeolitic surface.

Effects of preparation and experimental conditions on removal of phenol by surfactant-modified zeolites.

The removal of phenol from aqueous solutions using surfactant-modified clinoptilolite-rich tuffs (SMZ) prepared from two Mexican zeolitic tuffs (Chihuahua and Oaxaca) was investigated. Sodium homoionization of the zeolitic rocks was performed before they were modified with the surfactants: hexadecyltrimethylammonium chloride or bromide and bencylcetildimethylammonium chloride. The surfactants in the modified zeolitic materials were determined considering the total carbon in the samples. The phenol removal was determined in a batch system taking into consideration the different quantities of surfactants in the zeolitic tuffs, contact time, pH and initial phenol concentration. The phenol was determined in the aqueous solutions by UV/Vis spectroscopy. Results showed that the formation of a hemimicelle or admicelle on the zeolites depended on the initial surfactant concentration and they were responsible for the type of interactions between the phenol and the surfactant-modified zeolites. Phenol adsorption by the surfactant-modified zeolites was carried out in approximately three hours. Phenol adsorption data was best adjusted to the pseudo-second order kinetic model. Both, surface properties of the surfactant-modified zeolites and pH of solution play an important role in the removal of this pollutant from aqueous solutions and they are responsible for the type of mechanism involved.

Antibacterial behavior of silver-modified clinoptilolite-heulandite rich tuff on coliform microorganisms from wastewater in a column system.

The water disinfecting behavior of silver-modified clinoptilolite-heulandite rich tuff (ZSAg) as an antibacterial agent against coliform microorganisms from water in a continuous mode was investigated. Silver recovery from the disinfected effluents by the sodium-modified clinoptilolite-heulandite rich tuff (ZSNa) was also considered. Escherichia coli (ATCC 8739) and total coliform microorganisms, as indicators of microbiological contamination of water, were chosen to achieve the disinfection of synthetic wastewater or municipal wastewater. Ammonium (NH(4)(+)) and chloride (Cl(-)) ions were added to the synthetic wastewater as an interfering chemical species on the disinfection processes. The antibacterial activity of the ZSAg as a bactericide was measured by the coliform concentration as evaluated by the APHA method. The amount of silver in the disinfected effluents was determined using atomic absorption spectroscopy. The inactivation of the ZSAg was calculated from the breakthrough curves based on the model reported by Gupta et al. It was found that when the silver concentration in the effluent is less than 0.6 microg/mL, the bacterial survival percentage increased and the volume of disinfected water diminished. The total silver amounts found in the effluent at the end of the disinfection processes varied depending on the water treated (synthetic or municipal wastewater). The presence of NH(4)(+) ions in synthetic wastewater influent notably improved the disinfected water volume (zero NVC/100mL), in comparison to the disinfection of the same influent without NH(4)(+) ions. A contrary water disinfection behavior was observed in the presence of Cl(-) ions. The silver recovery does not depend on the mass of the sodium zeolitic bed according with the wastewater to be treated (synthetic or municipal wastewater) and the presence of NH(4)(+) or Cl(-) ions in the influent also influenced the silver recovery from wastewater. The ZSNa did not have antibacterial activity. Therefore the amount of bactericide agent (silver-modified natural zeolite), coliform microorganisms from water (E. coli or consort of coliform microorganisms) as well as the water quality (synthetic wastewater or municipal wastewater) influenced both the disinfection process and the silver recovery in a column system.

Evaluation of the sorption properties of a Mexican organo clinoptilolite-rich tuff for phenol and 4-chlorophenol.

A Mexican clinoptilolite-rich tuff was modified with the hexadecyltrimethyl ammonium (HDTMA) and used for the sorption of phenol and 4-chlorophenol. Whereas the zeolitic tuff had no affinity for phenol and 4-chlorophenol, the modified zeolite removed these organic compounds. The sorption behavior from aqueous solutions was studied by means of batch type and column experiments and isotherms were determined. It was found that the uptake was higher for 4-chlorophenol than for phenol.

Radon concentration levels in ground water from Toluca, Mexico.

Concentration levels of 222Rn have been analysed in water samples from deep wells of the aquifers around the City of Toluca, Mexico. The 222Rn source is the decay of 226Ra within the solid matrix of the aquifer. With a half life of 1600 years the 226Ra continuously releases 222Rn to the pores, from which it diffuses into the main body of water. This paper describes the methods used for sampling and measuring solubilized and 226Ra-supported 222Rn in the water samples, in order to evaluate possible health hazards due to the presence of radon in the drinking water supplies. The relationship of 222Rn with the hydrogeologic characteristics of the zone is also described. The analytical method involves laboratory extraction of 222Rn into toluene. Alpha disintegrations of 222Rn and contributions from short-lived daughters are counted by the liquid scintillation technique. The system was calibrated using a 226Ra standard solution. Results up to 11.3 Bq/l of 222Rn were obtained in the water samples.