In this work, we report on the synthesis and characterization of nanoporous bimetallic metal-organic frameworks (FeCo-BDC). Effects of synthesis time and temperature on the structures, morphology, and catalytic performance of FeCo-BDC were investigated. Scanning Electron Microscopy (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) were used to reveal the morphological and textural characteristics. The crystal structure and chemical composition of FeCo-BDC were determined by means of X-ray powder diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), X-ray Photoelectron Spectroscopy (XPS), and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) measurements. Interestingly, FeCo-BDC grew into the same crystal structure with different morphology in the temperature of 110–150 °C with 12–48 h. The heterogeneous catalytic activity of FeCo-BDC was tested to activate peroxydisulfate (PDS) and peroxymonosulfate (PMS) for removal of methylene blue (MB). The results found that FeCo-BDC synthesized at 150 °C with 24 h exhibited the best catalytic performance for PMS and obtained 100% of MB removal within 15 min. The abundant unsaturated metal active sites of Fe(II) and Co(II) in the skeleton of FeCo-BDC made a great contribution to the generation of sulfate (▪) and hydroxyl radicals (OH), which resulted in the excellent performance for MB degradation.

Huelva is a highly industrialized city in SW Spain hosting, among others, a Cu smelter, a phosphate fertilizer plant, a power plant, and oil refineries. This study aims to evaluate metal concentrations in lichens as bioindicators of atmospheric pollution in the impacted urban areas. Xanthoria parietina species from Huelva and nearby villages, as well as reference samples from remote, non-contaminated urban areas, were analyzed for trace elements (V, Cr, Mn, Co, Ni, Cu, Zn, Sr, As, Cd, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm, Er, Tm, Yb, Lu, Pb, Th, U) using Inductively Coupled Plasma-Mass Spectrometry; and for major elements (Ca, K, Mg, P, and S) by Inductively Coupled Plasma-Optical Emission Spectrometry after acid digestion.The metal composition of X. parietina exhibits spatial distribution patterns with extremely elevated concentrations (Co, Ni, Cu, Zn, As, Cd, Sb, Ba, Pb, U, and S) in the surroundings of the industrial estates to <1 km distance. Mean concentrations were significantly lower in the urban areas >1 km from the pollution sources. However, air pollution persists in the urban areas up to 4 km away, as the mean concentrations of Cu, Zn, As, Cd, Sb and S remained considerably elevated in comparison to the reference samples. Though rigorous source apportionment analysis was not the aim of this study, a good positive correlation of our results with metal abundances in ambient particulate matter and in pollution sources points to the Cu smelter as the main source of pollution. Hence, the severe air pollution affecting Huelva and nearby urban areas may be considered a serious health risk to local residents.

A biofilm reactor was designed with flat ceramic substrates to remove Co(II), Ni(II) and Zn(II) from industrial wastewater. The ceramics were made of clay and nano-rubber with high mechanical resistance. The surface of the ceramic substrate was modified with neutral fiber and nano-hydroxyapatite. A uniform and stable biofilm mass of 320 g with 2 mm of thickness was produced on the modified ceramic after 3 d. The micro-organisms were identified in the biofilm by polymerase chain reaction (PCR) method. Functional groups of biofilms were identified with a Fourier transform infrared spectrometer (FT-IR). Experiments were designed by central composite design (CCD) using the responsive surface method (RSM). The biosorption process was optimized at pH = 5.8, temperature = 22 °C, feed flux of heavy metal wastewater = 225 ml, substrate flow = 30 ml, and retention time = 7.825 h. The kinetic data was analyzed by pseudo first-order and pseudo second-order kinetic models. Isotherm models and thermodynamic parameters were applied to describe the biosorption equilibrium data of the metal ions on the biofilm-ceramic. The maximum biosorption efficiency and capacity of heavy metal ions were about 72% and 57.21 mg, respectively.

The cobalt ferrite-reduced oxidized graphene (CoFe2O4/rGO) catalyst was synthesized by hydrothermal method and characterized by Powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning electron microscope (SEM), Brunauere Emmette Teller (BET) and Hysteresis loop. For developing a new method of removing elemental mercury (Hg0) from flue gas, the effects of catalyst dosage, PMS concentration, solution pH and reaction temperature on the removal efficiency were investigated experimentally by using peroxymonosulfate (PMS) catalyzed by CoFe2O4/rGO at a self-made bubbling reactor. The average removal efficiency of Hg0 in a 30-min period reached 95.56%, when CoFe2O4/rGO dosage was 0.288 g/L, PMS concentration was 3.5 mmol/L, solution pH was 5.5 and reaction temperature was 55 °C. Meanwhile, based on the free radical quenching experiments, in which, ethyl alcohol and tert butyl alcohol were used as quenchers to prove indirectly the presence of •OH and SO4•−, the characterizations of catalysts and reaction products, and the existing results from other scholars. The reaction mechanism was proposed.

The study of aerosol dispersion characteristics in wastewater treatment plants (WWTPs) has attracted extensive attention. Oxidation ditch (OD) is a commonly implemented process during biological wastewater treatment. This study assessed the component characteristics, source apportionment, and exposure risks of aerosols generated from a WWTP using the OD process (AWO). The results indicated that the aeration part of oxidation ditch (ODA) exhibited the highest concentrations and proportions of the respiratory fractions (RF) of bacteria, Enterobacteriaceae, Staphylococcus aureus, and Pseudomonas aeruginosa. Some pathogenic or opportunistic-pathogenic bacteria and carcinogenic metal(loid)s were detected in the AWO. The source apportionment results indicated that the outdoor wastewater treatment processes and ambient air contributed to the constitution of the AWO. The indoor aerosols were mainly constituted by composition of the wastewater treatment process such as the sludge dewatering room (SDR). The pathogenic or opportunistic-pathogenic bacteria with eight genera (Colinsella, Dermatophilus, Enterobactor, Erycherichia-Shigella, Ledionella, Selenomonas, Xanthobacter, and Veillonella) were largely attributed to wastewater or sludge. The risk assessment suggested that inhalation was the main exposure pathway for aerosols (including bacteria and metal(loid)s). Additionally, As indicated the highest non-carcinogenic risks. Furthermore, As, Cd, and Co were associated with high carcinogenic risks. The ODA and sludge dewatering room (SDR) indicated the highest carcinogenic and non-carcinogenic risks of metal(loid)s, respectively. Thus, the AWO should be sufficiently researched and monitored to mitigate their harmful effects on human health, particularly with regard to the health of the site workers.

Metal flux measurements inform the mobility, potential bioavailability and risk of toxicity for metals in contaminated sediments and therefore is an important approach for sediment quality assessment. The binding and release of metals that contribute to the net flux is strongly influenced by the presence and behaviors of benthic organisms. Here we studied the effects of bioturbation on the mobility and efflux of metals from multi-metal contaminated sediments that inhabited by oligochaete worms or both worms and bivalves. Presence of bivalves enhanced the release of Mn, Co, Ni and Zn but not for copper and chromium, which is likely due to the high affinities of copper and chromium for the solid phase. Metals in the overlying water were primarily associated with fractions smaller than 10 kDa, and the fractionation of all metals were not affected by the presence of the bivalve. Metal fluxes attributed to different processes were also distinguished, and the bioturbation induced effluxes were substantially higher than the diffusive effluxes. Temporal variabilities in the total net effluxes of Mn, Co, Ni and Zn were also observed and were attributed to the biological activities of the bivalves. Overall, the present study demonstrated that the response of different metals to the same bioturbation behavior was different, resulting in distinct mobility and fate of the metal contaminants.

Crested ibis (Nipponia nippon), one of the rarest birds in the world, was almost extinct in the historically widespread areas partly due to the environmental pollution. Therefore, non-invasive indicators of feather, eggshell, and excrement were used to investigate the exposure of this endangered bird to eleven trace elements in this study. The results indicated that crested ibises under in situ and ex situ conservations were diversely exposed to trace elements, with higher exposure levels of As, Cd, and Mn in the wild, but higher exposure levels of Hg, Se, and Zn in the captive breeding center. In addition, concentrations of As, Co, Cr, and Ni were significantly greater in the sediments of three types of foraging habitats for wild crested ibis, but concentration of Se was greater in the soil of captive cages. Feather and eggshell of crested ibis exhibited a very consistent indication for most of the trace elements, and concentrations of almost all of the elements in the excrements were very consistent with the results in the environmental samples (sediments or soils). Concentrations of As, Hg, Mn, and Zn in feathers, and Mn and Zn in eggshells of wild and captive crested ibis were greater than those in other similar species. Moreover, As, Cd, Cu, and Mn concentrations in excrement of wild crested ibises were greater than that in captive individuals and other species, but Se and Zn concentrations in excrement of captive crested ibises were greater than that of the wild and other species. The present study provided evidence that both of the wild and captive crested ibis were exposed to trace elements, which may be harmful to their health.

This study investigated by the moss-bag approach the pattern of air dispersed elements in 12 coupled indoor/outdoor exposure sites, all located in urban and rural residential areas. The aims were to discriminate indoor vs. outdoor element composition in coupled exposure sites and find possible relation between moss elemental profile and specific characteristics of each exposure site.Elements were considered enriched when in 60% of the sites, post-exposure concentration exceeded pre-exposure concentration plus two folds the standard deviation. Of the 53 analyzed elements, 15 (As, B, Ca, Co, Cr, Cu, Mn, Mo, Ni, Sb, Se, Sn, Sr, V, Zn) were enriched in moss exposed outdoor, whereas a subset of 7 elements (As, B, Cr, Mo, Ni, Se, V) were enriched also in indoor moss samples. The cluster analysis of the sites based on all elements, clearly separated samples in two groups corresponding to mosses exposed indoor and outdoor, with the latter generally exceeding the first. Among outdoor sites, urban were most impacted than rural; whereas other factors (e.g., heating and cooking systems, building material, residence time and family life style) could affect element profile of indoor environments. Based on the indoor/outdoor ratio, As derived from outdoor and indoor sources, B, Mo and Se were enriched mostly in outdoor sites; Ni, Cr and V were specifically enriched in most indoor samples, supporting the presence of indoor emitting sources for these elements. A PCA of all indoor sites based on enriched elements and site characteristics showed that traffic affected indoor pollution in urban areas. The moss bag approach provided useful information for a global assessment of human exposure.

Absolute principal component score/multiple linear regression (APCS/MLR) and positive matrix factorization (PMF) were applied to a dataset consisting of 10 heavy metals in 300 surface soils samples. Robust geostatistics were used to delineate and compare the factors derived from these two receptor models. Both APCS/MLR and PMF afforded three similar source factors with comparable contributions, but APCS/MLR had some negative and unidentified contributions; thus, PMF, with its optimal non-negativity results, was adopted for source apportionment. Experimental variograms for each factor from two receptor models were built using classical Matheron's and three robust estimators. The best association of experimental variograms fitted to theoretical models differed between the corresponding APCS and PMF-factors. However, kriged interpolation indicated that the corresponding APCS and PMF-factor showed similar spatial variability. Based on PMF and robust geostatistics, three sources of 10 heavy metals in Guangrao were determined. As, Co, Cr, Cu, Mn, Ni, Zn, and partially Hg, Pb, Cd originated from natural source. The factor grouping these heavy metals showed consistent distribution with parent material map. 43.1% of Hg and 13.2% of Pb were related to atmosphere deposition of human inputs, with high values of their association patterns being located around urban areas. 29.6% concentration of Cd was associated with agricultural practice, and the hotspot coincided with the spatial distribution of vegetable-producing soils. Overall, natural source, atmosphere deposition of human emissions, and agricultural practices, explained 81.1%, 7.3%, and 11.6% of the total of 10 heavy metals concentrations, respectively. Receptor models coupled with robust geostatistics could successfully estimate the source apportionment of heavy metals in soils.

Bacterial endotoxins are a component of particulate matter (PM) with anticipated health implications, yet we know little about how host reception of endotoxin through toll-like receptor 4 (TLR4) is affected by its association with other PM components. Subsequently, we investigated the relationship between endotoxin concentration (recombinant Factor C (rFC) assay) and host recognition (HEK Blue-TLR4 NF-kB reporter cell line based assay) in various compositions of urban PM, including road traffic, industrial and urban green land use classes. While the assays did not correlate strongly between each other, the TLR4 reporter cell line was found to be better correlated to the IL-8 response of PM. Furthermore, the ability of the quantified endotoxin (rFC assay) to stimulate the TLR4/MD-2 complex was significantly affected by the urban land use class, where traffic locations were found to be significantly higher in bioactive endotoxin than the industrial and green locations. We subsequently turned our attention to PM composition and characterized the samples based on transition metal content (through ICP-MS). The effect of nickel and cobalt – previously reported to activate the hTLR4/MD-2 complex – was found to be negligible in comparison to that of iron. Here, the addition of iron as a factor significantly improved the regression model between the two endotoxin assays, explaining 77% of the variation of the TLR4 stimulation and excluding the significant effect of land use class. Moreover, the effect of iron proved to be more than a correlation, since dosing LPS with Fe²⁺ led to an increase up to 64% in TLR4 stimulation, while Fe²⁺ without LPS was unable to stimulate a response. This study shows that endotoxin quantification assays (such as the rFC assay) may not always correspond to human biological recognition of endotoxin in urban PM, while its toxicity can be synergistically influenced by the associated PM composition.