Batch experiments were conducted to study the effect of freeze-thaw frequency on the adsorption behavior of Pb²⁺ and Cd²⁺ and its related mechanisms. The results indicated that the adsorption capacities of Pb²⁺ and Cd²⁺ to the freeze-thaw treated soil were lower than those to the unfrozen soil, and with increasing freeze-thaw frequency, the adsorption capacities of them decreased. These were attributed to the fact that freeze-thaw cycles reduced pH value, CEC, organic matter content, and free iron oxide content of soil, and these soil properties presented negative correlations with freeze-thaw frequency. Freeze-thaw cycles reduced specific adsorption capacities of Pb²⁺ and Cd²⁺ and enhanced nonspecific adsorption ratios of Pb²⁺ and Cd²⁺ compared with the unfrozen soil. The higher freeze-thaw frequency, the higher nonspecific adsorption ratio was. However, the relationship between specific adsorption capacities of Pb²⁺ and Cd²⁺ and freeze-thaw frequency was opposite. Furthermore, the adsorption processes to the unfrozen and freeze-thaw treated soils were spontaneous, for Pb²⁺, its adsorption to soil was endothermal process, for Cd²⁺, on the contrary.

The establishment of a complementary grass cover on vineyard soils can promote sustainability of the affected environment. In this work, we used an acid vineyard soil with total Cu concentration 188 mg kg⁻¹ to study the influence of pine bark amendment on Lolium perenne growth and Cu uptake. The results indicate that the pine bark amendment did not cause a significant increase in the mass of the shoots of Lolium perenne, but favored the root biomass: 0.034 g for control and 0.061 g for soil samples amended with 48 g kg⁻¹ of pine bark. Moreover, the pine bark amendment decreased Cu concentration in both, shoots (50 mg kg⁻¹ for control soil and 29 mg kg⁻¹ for soil amended with 48 g kg⁻¹ pine bark) and roots (250 mg kg⁻¹ for control soil and 64 mg kg⁻¹ for soil amended with 48 g kg⁻¹ pine bark). The main factor responsible for these results was a significant decrease of the most mobile fractions of Cu in the soil. Those fractions were extracted using ammonium acetate, ammonium chloride, sodium salt of ethylene-diamine-tetraacetic acid (EDTA-Na), and diethylene-triamine-pentaacetic acid (DTPA).

Arsenate (As(V)) is an analog of phosphate (Pᵢ), and previous studies have shown that As(V) and Pᵢ are absorbed via the same transport systems in some organisms. However, little is known about which periplasmic phosphate-binding proteins (PBPs) of ABC-type Pᵢ transporters play major roles in As(V) uptake by cyanobacteria. In this study, the model cyanobacterium Synechocystis sp. PCC 6803 (Synechocystis) was chosen to study the ability of PBPs to discriminate between Pi and As(V). We found that As(V) and Pᵢ competed for uptake via Pᵢ transporters when Synechocystis was treated with As(V) and/or Pᵢ in short-term incubation. The As/P molar ratios of Synechocystis wild type (WT) and mutants (∆sphX, ∆pstS2, ∆sll0540, and ∆sphXpstS1) were measured, and they were significantly different with the order WT > ∆pstS2 > ∆sll0540 > ∆sphXpstS1 > ∆sphX. Furthermore, As(V) uptake by Escherichia coli strain Transetta expressing PBP genes, particularly sphX or sll0540, was significantly increased when PBP gene (pstS1, pstS2, sphX, or sll0540) was separately expressed in Transetta at the same level. Subsequent phylogenetic analyses of PBPs showed that SphX and Sll0540 belonged to the low-affinity PBPs, while PstS1 and PstS2 were clustered with the high-affinity PBPs. These results implied that As(V) was taken up via Pᵢ transporters, and the low-affinity PBPs, SphX and Sll0540, made a significant contribution to As(V) uptake.

The replacement of synthetic surface-active compounds (SACs) by their microbial counterparts is carving out a niche for themselves in the field of bioremediation. However, the high cost of microbial products has limited their application at a realistic scale. In the current study, several hydrocarbon-degrading microorganisms were assayed as potential SAC producers in low-cost liquid media. Only the strain CC10, placed within the class Actinobacteria, was able to produce emulsifying molecules by using a combination of sugarcane vinasse or crude glycerol (as cheap carbon substrates) with urea or peptone (as nitrogen sources). The emulsifying activity of the supernatants and the stability of emulsions formed with motor oil depended on the carbon and nitrogen sources. However, the biodegradability of these metabolites was only associated with the carbon substrate, and it was always higher than the two tested synthetic surfactants, sodium dodecyl sulfate and Triton X-100. Also, a positive linear association between emulsifying and lipase activities of the CC10 supernatants was detected (r = 0.781; p = 0.219), with the maximum activities detected in the glycerol-peptone supernatant. Interestingly, this supernatant was able to emulsify different oily substrates, a property that could be used to increase the efficiency of the treatment of effluents with high fat content.

In this study, graphene-based adsorbent was successfully prepared following a thermal treatment method. The prepared material, named as graphene-coated sand (GCS), was used as an adsorbent for the removal of Hg(II) ions from aqueous solutions. Structure, composition, and morphology of the GCS were characterized by Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), X-ray diffractometer (XRD), Raman spectroscopy, electron diffraction (ED) measurements, energy dispersive X-ray spectroscopy (EDX), surface area measurements, particle size, and zeta potential measurements, respectively. A batch adsorption method was used to assess the ability of GCS towards removal of Hg(II) ions from aqueous solutions. The results of batch studies revealed that the GCS required a pH value 6.0, contact time 120 min, and adsorbent dose of 200 mg to attain adsorption equilibrium. Langmuir, Freundlich, Temkin, and D-R adsorption isotherm models were employed to evaluate the isotherm constants and other parameters related to the adsorption process. The Hg(II) ions uptake by the GCS was found to follow Freundlich isotherm model with R ² value of 0.97695, under optimized conditions and at 40 °C with a maximum adsorption capacity of 299.40 mg/g. The adsorption process followed the second-order kinetic path. The thermodynamic parameters such as ΔH°, ΔS°, and ΔG° were also calculated which suggested that the adsorption processes of Hg(II) ions onto the GCS was endothermic and entropy favored. The values of ΔG° at 283, 303, and 313 K were − 1.10, − 0.025, and − 4.55 kJ, respectively, and ΔH°, ΔS° were calculated to be 26.60 kJ mol⁻¹ and ΔS° 1.35 J mol⁻¹ K⁻¹, respectively. The obtained results revealed that the prepared materials could be effectively and economically beneficial.

This study proposes a method, backpropagation (BP) neural network, for interpolating missing values in daily precipitation time series. Firstly, the BP neural network is adopted to interpolate missing daily rainfall data at three selected stations in Yantai, Shandong, China. Then, the temporal and spatial variations in precipitation extremes across Shandong are analyzed by utilizing the complete daily rainfall dataset derived from accurate propagation at 24 meteorological stations. The results show that the long-term trends in five selected extreme precipitation indices calculated from interpolated daily rainfall data are generally consistent with those from original nonmissing values. And the spatial patterns of trends in precipitation extremes also show better performance for BP neural network approach in interpolating missing daily rainfall gaps. Those suggest that this BP neural network algorithm can obtain a good fit in terms of space-time variability of regional precipitation extremes, in case that the correlation coefficients between the target stations with missing values and reference stations with complete daily rainfall dataset are relatively large. These findings could be crucial for investigating regional frequency of heavy rainfall and water resource management.

Adsorption of Rh(III) ions from the aqueous phase containing chloride ions was investigated batchwise using 1,3,5-triazine pentaethylenehexamine (TAPEHA) resin, which is highly resistant to strong acidic conditions. The effects of pH, temperature, initial concentration, and contact time on adsorption were examined. Rh(III) adsorption is favorable from the aqueous phase containing 3.0 and 0.1 M HCl. In both acidic cases, Langmuir is best fitting isotherm equation to system. The kinetics of Rh(III) adsorption on TAPEHA polymer was found to obey the pseudo-second-order kinetic equation, at both cases. Langmuir monolayer adsorption capacities were calculated as 327.03 and 113.76 mg/g in 3.0 and 0.1 M HCl, respectively. Experimental maximum adsorption capacities were measured as 198 and 100 mg/g in 3.0 and 0.1 M HCl, respectively. Due to different Rh(III) complexes with chlorine depending on acid concentrations, adsorption of Rh(III) from solutions containing 3.0 and 0.1 M HCl occurred via two different mechanisms; namely, ion exchange and surface complexation. The reuse of TAPEHA was also studied by column procedure, and the adsorption capacity of TAPEHA was not changed by using it five times. Adsorbed Rh(III) ions onto TAPEHA were completely eluted with thiourea 3% (w/v) in 1.0 M HCl. These findings showed that TAPEHA has a high resistance to acidic solutions and a higher Rh(III) uptake capacity than commercial adsorbents. Hence it can be used for rhodium recycling.

Sorption of antibiotics to clay minerals is a key process controlling their transport and fate in environment. In this study, the effects of pH, ionic strength, and Cu(II) on ofloxacin (OFL) sorption to kaolinite were investigated by batch sorption experiments. The results of sorption edge experiments suggested that OFL sorption to kaolinite was pH and ionic strength dependent. Cation exchange was a major contributor to the sorption of OFL⁺ to kaolinite. The decreased OFL sorption with increasing ionic strength indicated the formation of outer-sphere complexation. When solution pH was lower than 7.0, Cu-OFL complexes facilitated OFL sorption through electrostatic attraction or formation of kaolinite-Cu-OFL and kaolinite-OFL-Cu ternary surface complexes. However, existence of free Cu(II) cation in solution competed for sorption sites, and thus suppressed OFL sorption. When solution pH was higher than 7.0, Cu(II) existed as Cu(OH)₂, and the Cu-OFL complexes in aqueous phase and solid phase (precipitation) enhanced OFL removal efficiency from solution. The results imply that Cu(II) effects should be taken into account in the evaluation of OFL mobility in environment.

This is the first paper that describes the atmospheric sulfur dioxide (SO₂) and nitric acid (HNO₃) monitored with a good time-resolution at the summit (3776 m a.s.l.), which is located in the free troposphere, and southeastern foot (1284 m a.s.l.) of Mt. Fuji. Japan. During the summer of 2012, two analytical systems consisting mainly of a parallel-plate wet denuder and ion chromatograph operated simultaneously at both the sampling sites. All the samples collected at both the sampling sites contained detectable levels of sulfate from gas-phase SO₂ while the nitrate from gas-phase HNO₃ was detectable in 97.8% of air samples at the southeastern foot and 88.4% at the summit. The average concentrations of SO₂ and HNO₃ were, respectively, 0.061 ± 0.071 and 0.031 ± 0.020 ppbv at the summit (n = 672), and 0.347 ± 0.425 and 0.146 ± 0.070 ppbv at the southeastern foot (n = 1344) of Mt. Fuji. Both the acidic gases at the southeastern foot and the HNO₃ at the summit showed a diurnal pattern with daytime maxima and nighttime minima. Meanwhile, the SO₂ at the summit did not show a distinct shift, which indicates the SO₂ concentrations at the summit would be principally controlled by the advection of air parcel in the free troposphere.

The setting-up of anammox granules reactor is time-consuming and highly sensitive to the environment. Metal ions were reported to facilitate granulation; however, there is no report of a practical guide to metal ion application in anammox, especially relative to the effects of different ions at different concentrations on granulation. Adding recycle to reactors is important in treating industrial wastewater with high levels of NH₄ ⁺-N, but the optimum recycle ratio is still unclear. This study investigated the effect of Ca, Mg, Fe ions, their concentration, and recycle ratio of an upflow anaerobic sludge blanket reactor on anammox granulation as well as on reactor performance. The main physical properties of granules tested were sludge granulation rate, settling velocity, mixed liquor suspended solids (MLSS), mixed liquor volatile suspended solids/MLSS, and specific anammox activity (SAA)/nitrogen removal rate. The results demonstrated that introducing cations into cultivating mediums accelerates the anaerobic granulation process and improves specific anammox activity. In particular, Mg and Fe runs reached maximum SAAs with concentrations of 0.06 mmol/L and improved by ~ 25% of SAA compared with the control. SAAs of Ca runs were lower than those of Mg and Fe runs and showed a peak at a concentration of 0.03 mmol/L. In addition, recirculation enhanced the granulation. Granulation and retention of the anammox biomass were benefitted most when the recycle flow added was equal to the influent injection (noted as Q). Nitrogen removal also reached a maximum at Q, with removal efficiency of 97.3% with NH₄ ⁺-N and 98% with NO₂ ⁻-N. Thus, appropriately adding metal ions and recycle flow helped achieve quick setting-up and better performance. We also considered the relationship between four properties of granules tested and the performance of the reactor.