Hydrothermal Synthesis of Sodalite-Type N-A-S-H from Fly Ash to Remove Ammonium and Phosphorus from Water.

In this study, the hydrated sodium aluminosilicate material was synthesized by one-step hydrothermal alkaline desilication using fly ash (FA) as raw material. The synthesized materials were characterized by XRD, XRF, FT-IR and SEM. The characterization results showed that the alkali-soluble desilication successfully had synthesized the sodium aluminosilicate crystalline (N-A-S-H) phase of sodalite-type (SOD), and the modified material had good ionic affinity and adsorption capacity. In order to figure out the suitability of SOD as an adsorbent for the removal of ammonium and phosphorus from wastewater, the effects of material dosing, contact time, ambient pH and initial solute concentration on the simultaneous removal of ammonium and phosphorus are investigated by intermittent adsorption tests. Under the optimal adsorption conditions, the removal rate of ammonium was 73.3%, the removal rate of phosphate was 85.8% and the unit adsorption capacity reached 9.15 mg/L and 2.14 mg/L, respectively. Adsorption kinetic studies showed that the adsorption of ammonium and phosphorus by SOD was consistent with a quasi-secondary kinetic model. The adsorption isotherm analysis showed that the equilibrium data were in good agreement with the Langmuir and Freundlich model. According to thermodynamic calculations, the adsorption of ammonium and phosphorus was found to be a heat-absorbing and spontaneous process. Therefore, the preparation of SOD by modified FA has good adsorption properties as adsorbent and has excellent potential for application in the removal of contaminants from wastewater.

[Characteristics and Heavy Metal Adsorption Performance of Sewage Sludge-derived Biochar from Co-pyrolysis with Transition Metals].

To enhance the heavy metal cation adsorption capacity of sewage sludge-derived biochar in an aqueous medium with a high concentration of Ca2+, modified biochars were obtained from co-pyrolysis of sewage sludge and transition metal oxides (with a sewage sludge:transition metal mass ratio of 10:1), such as Fe2O3, MnO2, and ZnO. The properties of the modified biochars were characterized, and the Cd2+ adsorption effect of the modified biochars was determined as well. The H/C atom ratios of the modified biochars were all lower than 0.31, indicating that the transition metal oxides catalyzed the decomposition and volatilization of organic matter in sewage sludge. The majority of the added Fe and Mn remained in the modified biochars, and existed as a simple substance and oxide, respectively; while significant loss of Zn occurred. The pores of the modified biochars were mainly mesopores with an average pore size of approximately 3.8 nm, and the specific surface area of the modified biochars was larger than 50 m2·g-1. When the initial Cd2+ concentration was increased from 0 mg·L-1 to approximately 200 mg·L-1, the Cd2+ adsorption capacity of the Fe-modified biochar declined from 43.17 mg·g-1 to 27.88 mg·g-1, which was still higher than that of the unmodified biochar by at least 10 mg·g-1. In aqueous media with a high concentration of Ca2+, the Fe-modified biochar showed better Cd2+ adsorption performance; thus, compared to MnO2 and ZnO, Fe2O3 was the best choice to enhance the heavy metal adsorption performance of the sewage sludge-derived biochar.

New molecular method to detect denitrifying anaerobic methane oxidation bacteria from different environmental niches.

The denitrifying anaerobic methane oxidation is an ecologically important process for reducing the potential methane emission into the atmosphere. The responsible bacterium for this process was Candidatus Methylomirabilis oxyfera belonging to the bacterial phylum of NC10. In this study, a new pair of primers targeting all the five groups of NC10 bacteria was designed to amplify NC10 bacteria from different environmental niches. The results showed that the group A was the dominant NC10 phylum bacteria from the sludges and food waste digestate while in paddy soil samples, group A and group B had nearly the same proportion. Our results also indicated that NC10 bacteria could exist in a high pH environment (pH9.24) from the food waste treatment facility. The Pearson relationship analysis showed that the pH had a significant positive relationship with the NC10 bacterial diversity (p<0.05). The redundancy analysis further revealed that the pH, volatile solid and nitrite nitrogen were the most important factors in shaping the NC10 bacterial structure (p=0.01) based on the variation inflation factors selection and Monte Carlo test (999 times). Results of this study extended the existing molecular tools for studying the NC10 bacterial community structures and provided new information on the ecological distributions of NC10 bacteria.

Development, modification, and application of low-cost and available biochar derived from corn straw for the removal of vanadium(v) from aqueous solution and real contaminated groundwater.

In this work, a low-cost and available material for use as a permeable reactive barrier (PRB) to prevent vanadium in groundwater from leaking into river water was developed. Three modified biochars were prepared from available corn straw pretreated with CsCl, Zn(ii), and Zr(iv) to enhance ion exchange capacity (IEC) and specific surface area, and were designated as Cs-BC, Zn-BC, and Zr-BC, respectively. These materials were characterized via IEC, N2 adsorption-desorption, Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) analyses. The Langmuir isotherm model could be applied for the best fit for the adsorption data of Cs-BC and Zr-BC, indicating that vanadium(v) sorption occurred in a monolayer. The vanadium(v) adsorption capacities of Cs-BC, Zn-BC, and Zr-BC were 41.07, 28.46, and 23.84 mg g-1, respectively, which were 3.22-5.55 times higher than that of commercial activated carbon (AC) (7.40 mg g-1), probably because of their higher IECs and specific surface areas after modification. In addition, no heavy metal leaching was found from the modified biochars during the adsorption processes when pH > 2. According to the FTIR and XRD patterns, the adsorption mechanism of Cs-BC and Zr-BC was ion exchange, whereas for Zn-BC, it was mainly surface precipitation and electrostatic attraction. The adsorption of vanadium(v) onto the modified biochars was independent of pH in the range of 4.0 to 8.0. Furthermore, the removal efficiency of the vanadium(v) in real contaminated groundwater from the catchment of the Chaobei River by Zn-BC reached 100% at a dose of 4 g L-1. Hence, modified biochars are promising PRB filling materials for removing vanadium(v) from contaminated groundwater.

Fugitive halocarbon emissions from working face of municipal solid waste landfills in China.

Halocarbons are important anthropogenic greenhouse gases (GHGs) due to their long lifetime and large characteristic factors. The present study for the first time assessed the global warming potential (GWP) of fugitive halocarbon emissions from the working face of landfills in China. The national emissions of five major halocarbons (CFC-11, CFC-113, CH2Cl2, CHCl3 and CCl4) from the working face of municipal solid waste landfills in China were provided through observation-based estimations. The fluxes of halocarbons from working face of landfills were observed much higher than covered cells in landfills hence representing the hot spots of landfill emissions. The annual emissions of the halocarbons from landfills in China were 0.02-15.6kt·y-1, and their GWPs were 128-60,948kt-CO2-eq·y-1 based on their characteristic factors on a 100-year horizon. CFC-113 was the dominant species owing to its highest releasing rate (i.e. 15.4±19.1g·t-1) and largest characteristic factor, resulting in a GWP up to 4036±4855kt-CO2-eq·y-1. The annual emissions of CFC-113 from landfills (i.e. 0.61kt·y-1) made up ∼76% of the total national CFC-113 emissions. The GWPs of halocarbons were estimated ∼14.4% of landfill methane emissions. Therefore, fugitive halocarbons emissions from working face are significant sources of GHGs in landfill sites in China, although they comprise a small fraction of total landfill gases.

Theoretical insight into the solvent effect of H2O and formamide on the cooperativity effect in HMX complex.

The cooperativity effects of the H-bonding interactions in HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane)∙∙∙HMX∙∙∙FA (formamide), HMX∙∙∙HMX∙∙∙H2O and HMX∙∙∙HMX∙∙∙HMX complexes involving the chair and chair-chair HMX are investigated by using the ONIOM2 (CAM-B3LYP/6-31++G(d,p):PM3) and ONIOM2 (M06-2X/6-31++G(d,p):PM3) methods. The solvent effect of FA or H2O on the cooperativity effect in HMX∙∙∙HMX∙∙∙HMX are evaluated by the integral equation formalism polarized continuum model. The results show that the cooperativity and anti-cooperativity effects are not notable in all the systems. Although the effect of solvation on the binding energy of ternary system HMX∙∙∙HMX∙∙∙HMX is not large, that on the cooperativity of H-bonds is notable, which leads to the mutually strengthened H-bonding interaction in solution. This is perhaps the reason for the formation of different conformation of HMX in different solvent. Surface electrostatic potential and reduced density gradient are used to reveal the nature of the solvent effect on cooperativity effect in HMX∙∙∙HMX∙∙∙HMX. Graphical abstract RDG isosurface and electrostatic potential surface of HMX∙∙∙HMX∙∙∙HMX.

Structure and diversity of bacterial communities in two large sanitary landfills in China as revealed by high-throughput sequencing (MiSeq).

Landfill disposal has been considered as a very economically viable management practice for municipal solid waste in mainland China. However, insufficient knowledge of the bacterial community structure and diversity in landfills hampers effectively landfill disposal. In this study, the structure and diversity of bacterial communities in two large sanitary landfills in northern and western parts of China were examined by high-throughput sequencing via a MiSeq platform. Nearly 1million effective sequences (981,575) were obtained from the 20 samples collected from four independent sites with different deposit depths (up to 18m). These sequences contained high amount of operational taxonomic units (OTUs), 2511-9955 OTUs at a cutoff level of 3% and a sequencing depth of 23,928. Firmicutes, Bacteroidetes and Proteobacteria were the most abundant phyla in the samples. Clear geographical differences between the sampling sites were revealed by nonmetric multidimensional scaling. Most of the samples from the same sampling site could be clustered together. Thus, the heterogeneity of the bacterial community structures was more significantly affected by the sampling site than by sampling depth. Redundancy analysis results suggested that seven physicochemical attributes, namely NH4+-N, NO2--N, moisture, pH, dissolved organic carbon (DOC), SO42- and total Cu element, significantly affected the bacterial community structures (P<0.001) based on variance inflation factor selection. Among these attributes, NH4+-N, NO2--N, moisture, pH and DOC were the most important parameters influencing the bacterial community structures (P<0.05). This study elucidated the structure and diversity of bacterial communities in landfills and discerned the relationships between bacterial community structures and physicochemical attributes. To the best of our knowledge, this study is among the first to characterize bacterial community structures in landfills by using this novel high-throughput sequencing approach.

Health risk impacts analysis of fugitive aromatic compounds emissions from the working face of a municipal solid waste landfill in China.

Aromatic compounds (ACs) emitted from landfills have attracted a lot of attention of the public due to their adverse impacts on the environment and human health. This study assessed the health risk impacts of the fugitive ACs emitted from the working face of a municipal solid waste (MSW) landfill in China. The emission data was acquired by long-term in-situ samplings using a modified wind tunnel system. The uncertainty of aromatic emissions is determined by means of statistics and the emission factors were thus developed. Two scenarios, i.e. 'normal-case' and 'worst-case', were presented to evaluate the potential health risk in different weather conditions. For this typical large anaerobic landfill, toluene was the dominant species owing to its highest releasing rate (3.40±3.79g·m-2·d-1). Despite being of negligible non-carcinogenic risk, the ACs might bring carcinogenic risks to human in the nearby area. Ethylbenzene was the major health threat substance. The cumulative carcinogenic risk impact area is as far as ~1.5km at downwind direction for the normal-case scenario, and even nearly 4km for the worst-case scenario. Health risks of fugitive ACs emissions from active landfills should be concerned, especially for landfills which still receiving mixed MSW.

Adsorption of cadmium by biochar derived from municipal sewage sludge: Impact factors and adsorption mechanism.

Static equilibrium experiments were carried out to investigate the impact factors and the mechanism of cadmium adsorption on biochar derived from municipal sewage sludge. An appropriate dosage of biochar is sufficient; in the experiment, 0.2% is the optimal dosage for the largest removal capacity, while the removal capacity of biochar reduces with the increasing dosage. pH is another dominant factor of the adsorption process. The removal capacity of biochar is lower than 20 mg·g(-1) when the solution initial pH is lower than 2 pH units, comparatively retaining more than 40 mg·g(-1) at the solution initial pH higher than 3 pH units. Temperature has weak influence on the adsorptive performance. The main mechanism of the adsorption process of biochar for cadmium mainly involves (1) surface precipitation by forming insoluble cadmium compounds in alkaline condition, and (2) ion exchange for cadmium with exchangeable cations in the biochar, such as calcium ions.