Using hybrid packing materials in biofiltration systems takes advantage of both the inorganic and organic properties offered by the medium including structural stability and a source of available nutrients, respectively. In this study, hybrid mixtures of compost with either lava rock or biochar in four different mixture ratios were compared against 100% compost in a methane biofilter with active aeration at two ports along the height of the biofilter. Biochar outperformed lava rock as a packing material by providing the added benefit of participating in sorption reactions with CH4. This study provides evidence that a 7:1 volumetric mixture of biochar and compost can successfully remove up to 877 g CH4/m3·d with empty-bed residence times of 82.8 min. Low-affinity methanotrophs were responsible for the CH4 removal in these systems (KM(app) ranging from 5.7 to 42.7 µM CH4). Sequencing of 16S rRNA gene amplicons indicated that Gammaproteobacteria methanotrophs, especially members of the genus Methylobacter, were responsible for most of the CH4 removal. However, as the compost medium was replaced with more inert medium, there was a decline in CH4 removal efficiency coinciding with an increased dominance of Alphaproteobacteria methanotrophs like Methylocystis and Methylocella. As a biologically-active material, compost served as the sole source of nutrients and inoculum for the biofilters which greatly simplified the operation of the system. Higher elimination capacities may be possible with higher compost content such as a 1:1 ratio of either biochar or lava rock, while maintaining the empty-bed residence time at 82.8 min.

The environmental contaminant, especially pesticides, threatened the amphibian population. In this assay, the enantioselective behavior of cyproconazole on Rana nigromaculata was studied. We found LC50 (lethal concentration causing 50% mortality) of 4-enantiomers was nearly twice as 3-enantiomers in 96 h acute toxicity test. Besides, the significant considerable variation of oxidative stress and LDH (lactic dehydrogenase) induced by the four enantiomers indicated that cyproconazole could enantioselectively affect enzymes in tadpoles. Bioaccumulation experiments showed the order of cyproconazole in the tadpoles was 4-enantiomers>3- enantiomers>2- enantiomers>1- enantiomers during the exposure for 28d. In tissue distribution test, cyproconazole was formed and accumulated in order of 4-enantiomers>2-enantiomers>3- enantiomers>1- enantiomers, except that in the gut. During the elimination experiment, cyproconazole was rapidly eliminated by 95% within the only 24 h. These results suggested that the influence of enantioselective behavior should consider when assessing ecological risk of chiral pesticides to amphibians.

The occurrence, distribution and removal efficiencies of organophosphorus flame retardants (OPFRs) and metals were examined in a municipal landfill leachate treatment system in Guangzhou, China. Five OPFRs and thirty-five metals were detected in wastewater samples collected at different treatment stages. ∑OPFRs was reduced from 4807.02 ng L−1 to 103.91 ng L−1 through the treatment system, with close to 98% removed from the dissolved phase. Tris(clorisopropyl) phosphates (TCPPs) dominated through the treatment process and accounted for over 80% and 50% of ∑OPFRs at the influent and the effluent, respectively. TCPPs were most efficiently removed (98.6%) followed by tris(2-chloroethyl) phosphate (TCEP) (96.6%) and triphenyl phosphate (TPP) (88.5%). For metals, Fe, Cr, and Rb were dominant in the raw leachate, detected at 7.55, 2.82, and 4.50 mg L−1, respectively. Thirteen regulated heavy metals – including eight major pollutants (i.e., As. Cd, Cr, Cu, Hg, Ni, Pb, and Zn) – have been detected in all wastewater samples at sub-mg L−1 levels. Over 99.5% removal was achieved for Cr, Ni, and Fe, and close to 95% removal efficiency was observed for Rb. For the eight major heavy metals, over 99% removal was observed; the only exception was Cu, which was removed at 89%. It was found that microfiltration/reverse osmosis was critical for the removal of OPFRs and heavy metals while the core biological treatment played a minor role towards their removal. Remobilization of Co, Cu, Fe, Hg, Mn, Ni, Sb, and Sr from the returned sludge occurred during the second denitrification, indicating the need for additional post-biological process for effective removal of both contaminants. This study highlights the critical need to develop cheap, effective treatment technologies for contaminants-laden leachate generated from open dumps and under-designed landfills.

In situ photocatalytic degradation of dissolved organic matter (DOM) of stormwater runoff can efficiently improve the aquatic environment quality and relieve the wastewater treatment pressure. In this work, photocatalytic degradation of DOM in TiO₂ (AEROXIDE® P-25) photocatalyst under illumination of ultraviolet (UV) light was carried out, considering the influence of various factors like TiO₂ dosage, solution pH along with the existence of co-existing ions (Cu²⁺ and H₂PO₄⁻). Generally, the variations of dissolved organic carbon (DOC), UV-based parameters and peak intensities of fluorescent constituents with UV exposure time fitted perfectly with the pseudo-first-order kinetics model. The total DOM removal efficiency was affected by diversiform factors like adsorption capacity of TiO₂, UV light utilization efficiency, reactive free radicals produced and the influence of co-existing ions. The results of fluorescence excitation-emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) modeling demonstrated that all the photodegradation rates for three identified fluorescent constituents (protein-like constituent 1 and 3, humic-like constituent 2) were faster than UV-absorbing chromophores, suggesting the DOM molecules in urban stormwater runoff contained much more π*-π transition structures. In addition, H₂PO₄⁻ ions affected the photodegradation of DOM by capturing positive holes (h⁺) and hydroxyl radical (·OH), whereas Cu²⁺ ions were inclined to generate Cu-protein complexes that were more difficult to degrade than the other Cu-DOM complexes. This study supplied novel insights into the photocatalytic degradation mechanism of individual organic constituent in urban stormwater runoff and explored the influences of co-existing contaminants on their adsorption-photocatalysis processes.

Genotoxic compounds, as common contaminants of the air environment, are of interest in air pollution monitoring. There are several methods to determine the level of these contaminants in different localities, many of which may be difficult to access with the use of conventional active and passive samplers. In the present study, the needles Pinus mugo Turra and Picea abies were used to monitor sampling localities in Austria, Slovakia, and the Czech Republic. Needles were extracted and chemical analysis and the genotoxicity bioassay SOS chromotest were used to obtain complex information about the chemical mixture of pollutants present and their genotoxic effects. The SOS chromotest method was optimized by using a CPRG chromogenic substrate to reduce the false positive genotoxic effect of needle extracts. Pinus mugo Turra and Picea abies were identified as suitable passive sampling matrices for long-term air monitoring using the same plants sampled at the same time. The presented study brings an innovative method for the fast screening and identification of localities loaded by genotoxic active air contaminants.

Municipal wastewater treatment plants (WWTPs) are important in the migration and transformation of perfluoroalkyl substances (PFASs) in water bodies. Six municipal WWTPs located in the upper reaches of the Guanting reservoir, along the Yanghe River, were sampled from November 2016 to July 2017. Influents, effluents, and activated sludge solutions were sampled and the concentrations of 17 PFASs were analyzed. Perfluorobutanoic acid (PFBA), Perfluorooctanoic acid (PFOA), Perfluorohexanoic acid (PFHxA), Perfluoropentanoic acid (PFPeA), Perfluorobutane sulfonat (PFBS) and Perfluorooctane sulfonate (PFOS) accounted for more than 90% of these. Seasonal variations in PFASs in influent directly influenced concentrations in supernatant and effluent. The annual average PFAS concentrations were 46.4, 45.1, and 38.5 ng L⁻¹ in influent, supernatant, and effluent, respectively, indicating that WWTPs do not efficiently remove PFASs from wastewater. Annual average PFAS removal efficiencies differed among WWTPs, were influenced primarily by the treatment process used at each, and followed the order Cyclic Activated Sludge System (CASS, 32.2%) > Orbal Oxidation Ditch (OD, 17.5%) > Anaeroxic–Anoxic–Oxic (A²/O, −1.49%). Short-chain PFASs were removed significantly more efficiently in the CASS compared to the other systems. These results can show how traditional wastewater treatment plants can help remove PFASs from the environment.

Benzene, toluene and xylene (BTX) belong to an important group of aromatic volatile organic compounds (VOCs) that are usually emitted from various sources. BTX play a vital role in the tropospheric chemistry as well as pose health hazard to human beings. Thus, an investigation of ambient benzene, toluene and xylene (BTX) was conducted at urban and rural sites of Gorakhpur for a span of one year in order to ascertain the contamination levels. The sampling of BTX was performed by using a low-flow SKC Model 220 sampling pump equipped with activated coconut shell charcoal tubes with a flow rate of 250 ml/min for 20–24 h. The analysis was in accordance with NIOSH method 1501. The efficiency of pump was checked weekly using regulated rotameters with an accuracy of ±1%. The samples were extracted with CS₂ with occasional agitation and analyzed by GC-FID. The total BTX concentration ranged from 3.4 μg m⁻³ to 45.4 μg m⁻³ with mean value 30.95 μg m⁻³ and median 24.8 μg m⁻³. The mean concentration of total BTX was maximum during winter (39.3 μg m⁻³), followed by summer (28.4 μg m⁻³) and monsoon season (25.1 μg m⁻³). The mean concentration of BTX at urban site (11.8 μg m⁻³) was higher than that at rural site (8.8 μg m⁻³). At both the sites, T/B and X/B ratios were highest in monsoon and lowest in winters. Toluene against benzene plot shows R² value of 0.96 and 0.49 at urban and rural sites respectively. Higher R² value at urban site clearly indicates similar sources of emission for benzene and toluene. At both the sites, the estimated integrated lifetime cancer risk (ILTCR) for benzene exceeded the threshold value of 1E-06 whereas the individual hazard quotients (HQ) for BTX did not exceed unity at any of the sites.

Biochar has been used for immobilizing heavy metals in soils due to its abundant surface functional groups and mineral components. However, as carbonaceous material, biochar in soils is susceptible to natural aging, which could alter its structural properties and ability to retain heavy metals. In this study, the impacts of pre- and post-application aging on the properties of dairy manure and sawdust biochars and the significance of different mechanisms of complexation with surface functional groups and mineral precipitation for Cd immobilization in soils were investigated. The simulated natural aging including 25 dry-wet cycles and 25 freeze-thaw cycles decreased the pH of biochar from 8.2 to 10.7 to 7.5–9.7 while increased the release of dissolved organic carbon from 4.1 to 10.9 to 5.9–21.3 mg L⁻¹, O/C ratios from 0.09 to 0.30 to 0.17–0.33, and O-containing functional groups, especially -OH and -C=O groups. New minerals such as CaC₂O₄ and MgO·MgCO₃ were formed during freeze-thaw cycles. The capacity of pre-aged biochars to immobilize Cd in soils decreased from 57-70% to 53–63%, compared to that of fresh biochar, which was mainly due to decrease of CdCO₃ or Cd₃(PO₄)₂ precipitation as evidenced by XRD and MINTEQ modeling. By contrast, post-aging of biochar application in soil with dry-wet and freeze-thaw cycling had little effect on the biochar's alkalinity while increased the O/C ratios from 0.10 to 0.24 to 0.15–0.27 and intensity of O-containing functional groups. The immobilization capacity of biochars for Cd in soil increased from 44-68% to 59–73% due to the enhanced surface complexation with O-containing groups. In short, biochar subjected to pre-aging had a reduced capacity to immobilize Cd, while biochars with post-aging in soil increased its Cd immobilization capacity as a soil amendment.

Excessive amounts of fluoride in drinking groundwater are harmful to human health, but the mechanisms responsible for fluoride enrichment in groundwater are not fully understood. Samples from two neighboring areas with endemic fluorosis were collected to test the hypothesis that there are distinctly different mechanisms responsible for the enrichment of fluoride in these groundwater. Hydrochemistry, stable isotopes and geochemical simulation were conducted together to investigate the fluoride spatial distribution and the diversity of responsible mechanisms. Our results showed that the spatial distributions of fluoride are different: I) high [F] in fresh shallow groundwater (SGQJ) and II) medium [F] in fresh to brackish deep groundwater (DGQJ) in the Qiji area; and III) medium [F] in brackish shallow groundwater (SGYH) and IV) low [F] in fresh deep groundwater (DGYH) in the Yanhu area. We also found that the fluoride concentration in groundwater is primarily controlled by the dissolution equilibrium of fluorite, as suggested by the correlation between [F] and [Ca]. However, there are other significant mechanisms: 1) for SGQJ, fluoride-bearing minerals (such as fluorite) dissolution, along with moderate evaporation, cation exchange and the more alkaline conditions are the driving factors; 2) for SGYH, the contributing factors are strong evaporation, the salt effect, dissolution of evaporites, gypsum and dolomite, bicarbonate-fluoride competition and anthropogenic activity; 3) for DGQJ, cation exchange, alkaline conditions and competitive adsorption are major factors; and 4) dolomite dissolution promotes the [F] increase in DGYH. Our findings suggest that the hydrogeochemical conditions play key roles in the enrichment of fluoride and that caution should be taken in the future when evaluating fluoride occurrence in groundwater, even in nearby areas.

Tetracyclines are a class of antimicrobials frequently found in the environment, and have promoted the proliferation of antibiotic resistance. An unanswered research question is whether tetracycline sorbed to soils is still bioavailable to bacteria and exerts selective pressure on the bacterial community for the development of antibiotic resistance. In this study, bioreporter E. coli MC4100/pTGM strain was used to probe the bioavailability of tetracycline sorbed by smectite clay, a class of common soil minerals. Batch sorption experiments were conducted to prepare clay samples with a wide range of sorbed tetracycline concentration. The bioreporter was incubated with tetracycline-sorbed clay at different clay/solution ratios and water contents, as well as using dialysis tubings to prevent the direct contact between bacterial cells and clay particles. The expression of antibiotic resistance genes from the bioreporter was measured using a flow cytometer as a measurement of bioavailability/selective pressure. The direct contact of bioreporter cells to clay surfaces represented an important pathway facilitating bacterial access to clay-sorbed tetracycline. In clay-water suspensions, reducing solution volume rendered more bacteria to attach to clay surfaces enhancing the bioavailability of clay-sorbed tetracycline. The strong fluorescence emission from bioreporter cells on clay surfaces indicated that clay-sorbed tetracycline was still bioavailable to bacteria. The formation of biofilms on clay surfaces could increase bacterial access to clay-sorbed tetracycline. In addition, desorption of loosely sorbed tetracycline into bulk solution contributed to bacterial exposure and activation of the antibiotic resistance genes. Tetracycline sorbed by soil geosorbents could exert selective pressure on the surrounding microbial communities via bacterial exposure to tetracycline in solution from desorption and to the geosorbent-sorbed tetracycline as well.