Fluoride contents in commonly used commercial phosphate fertilizers and their potential risks in China.

The application of phosphate fertilizer is an important source of anthropogenic fluoride in agricultural soil. However, relatively few studies have examined the fluoride content of phosphate fertilizers, and that has limited our understanding of the phosphate fertilizer contribution to soil fluoride accumulation and distribution. To examine this problem, we first quantified the total fluoride (TF) and water-soluble fluoride (WF) contents of six of the most commonly used commercial phosphate fertilizers in China (potassium dihydrogen phosphate (MKP), calcium superphosphate (SSP), monoammonium phosphate (MAP), diammonium phosphate (DAP), ternary compound fertilizer (NPK), and water-soluble macroelement fertilizer (WSF)). After calculating the [P2O5]/TF ratio for each of those fertilizers, we used those ratios and the average P2O5 application per crop of five typical crops grown in China (apples, greenhouse vegetables, wheat, corn, and rice) to estimate the annual fluoride accumulations in their soils after application of each type of phosphate fertilizer. Among the six fertilizer types, SSP, DAP, and NPK had much higher total fluoride and water-soluble fluoride contents than MKP, MAP, and WSF had. During crop production, the risk of fluoride accumulation was lower with MKP, MAP, and WSF (high [P2O5]/TF ratios) and higher with SSP, DAP, and NPK (low [P2O5]/TF ratios), especially in cash crops (fruit and greenhouse vegetables), which traditionally have unreasonably high P2O5 applications. Based on our findings, we proposed steps that should be taken to help effectively mitigate fluoride accumulation in China's agricultural soils.

Utilization of KOH-modified fly ash for elimination from aqueous solutions of potentially toxic metal ions.

Long-term accumulation of toxic heavy metals in the environment was a potential hidden danger. High energy consumption, complicated operation and low adsorption capacity were the disadvantages of most current adsorbents. This study used one-step modification of fly ash (FA) by low-temperature melting method with KOH as the activator to generate modified fly ash (KFA) with high adsorption capacity to remove heavy metals from aqueous solutions. Various characterization results revealed a destruction that occurred on the surface structure of adsorbent, 12 times increase in specific surface area, and metal ions were successfully adsorbed onto KFA surface. Furthermore, adsorption proceeded most favorably at pH of 5, the presence of ionic strength and co-existing cations significantly influenced the adsorption effects. The description of adsorption data was more suitable by pseudo-second-order kinetics and Langmuir isotherm models. And in single system at 25 °C, for Pb(II), Cu(II), and Cd (II), the qm were 337.41, 310.09 and 125.00 mg·g-1. However, in ternary system, the qm decreased for all three ions in the order Pb(II) > Cu(II) > Cd(II), which was different from the law in single system, and the Pb(II) adsorption was found to have a significant inhibited effect on adsorption of Cd(II) and Cu(II). The adsorption mechanisms including ion exchange, electrostatic attraction and complexation were revealed. And by exploring the bioaccessibility of absorbed heavy metals in four simulated digestive fluids, it was found that KFA could load heavy metal ions and enable their release in organisms and other aquatic environments, which provided the possibility for subsequent related studies. Therefore, KFA with low energy consumption and high adsorption capacity is equipped a prospective development space on removing heavy metals from wastewater.

The role of available nitrogen in the adsorption of polystyrene nanoplastics on magnetic materials.

Several studies have been conducted on nanoplastics (NPs). However, few studies have investigated the complexity of the interactions between NPs and other aqueous pollutants in multi-solute media. In this study, the adsorption of polystyrene nanoplastics (PSNPs) on magnetic materials (MS) in the presence of available nitrogen (AN) was studied. The results demonstrated that the adsorbed amount of PSNPs increased in the presence of ammonium nitrogen (NH4+-N), whereas no significant difference was detected on the adsorbed amount of PSNPs using nitrate nitrogen (NO3--N) as a cosolute. The increase in the adsorbed amount of PSNPs was attributed to the formation of an MS-PSNPs-NH4+-N complex. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and zeta potential analyses indicated that the PSNPs with NH4+-N as a cosolute can be bound on the MS surfaces. Moreover, the change in the PSNPs amount adsorbed by MS depends on the valence state, electronegativity of the coexisting ions, and the surface properties and functional groups of PSNPs. Additionally, the ionic strength, dissolved organic matter, solution pH, metal cations and the subsequent release of MS-coated PSNPs and NH4+-N changed considerably in different aquatic systems and artificial nitrating fluids. Among different natural aquatic systems, the PSNPs adsorption on MS was excellent in lake water. The results indicate high potential for the attachment of PSNPs to MS in the presence of AN and further deepen the understanding of removing NPs using magnetic materials in aqueous systems with various coexisting contaminants.

Fluoride accumulation characteristics in a northern China apple orchard that has had long-term phosphate fertilization.

Phosphate fertilizer can cause fluoride accumulation in the soil and excessive fluoride poses potential risks to soil and food crop safety. However, the effects of fertilization on soil and fruit fluoride accumulations through long-term positioning trials, especially in high-fertilizer application situations such as apple orchards, have received little attention. To close this knowledge gap, we conducted a field experiment to demonstrate the effects among five long-term (13-year) fertilizer treatments on fluoride accumulations at different soil depths and in the fruits of an apple orchard in Baishui, Shaanxi, China. The five treatments included no fertilization (CK); manure application (M); nitrogen and phosphate fertilization (NP); nitrogen, phosphorus, and potassium fertilization (NPK); and groundcover with nitrogen and phosphate fertilization (GNP). The results confirmed that all phosphate fertilizer treatments (NP, NPK, and GNP) had significant increases in total fluoride (TF) and water-soluble fluoride (WF) accumulations in the topsoil (0-20 cm). Among the phosphate fertilizer treatments, NP topsoil accumulated the most TF and WF, 79.4 and 7.7 mg kg-1 more than CK, respectively, and an average annual TF increase of 6 mg kg-1. However, the M treatment both experienced reduced fluoride content in the topsoil and had TF and WF contents 8.1 and 0.67 mg kg-1 lower than CK, respectively. There was no significant difference between all fertilizer treatments and CK in apple fluoride content. Furthermore, TF and WF accumulated mainly in the topsoil and the differences in soil fluoride content among the treatments decreased with soil depth. These findings showed that long-term phosphate fertilization increases the risk of fluoride accumulation in orchard topsoil. Altogether, these results improve the understanding of the characterization of soil and fruit fluoride accumulations in apple orchards under long-term fertilizer conditions and provide new insights into the use of manure as a possible alternative fertilization strategy that reduces fluoride accumulation.

Dissolved greenhouse gas emissions from agricultural groundwater irrigation in the Guanzhong Basin of China.

While evidence indicates that groundwater is a potential source for greenhouse gas (GHG) emissions, information for such emissions in groundwater used for irrigation is lacking. Based on 23 wells in the mid-western Guanzhong Basin of China, we investigated the dissolved CO2, N2O, and CH4 distributions in groundwater, their relationships with water indicators, and emission fluxes during flood irrigation. We found zero methane, but CO2 and N2O were 30 and 25 times, respectively, supersaturated compared to atmospheric concentrations. Dissolved N2O in groundwater was positively correlated with NO3--N (P = 0.009), while CO2 depended mainly on low pH and high dissolved inorganic carbon. The CO2 and N2O emission fluxes detected in wellheads, especially in shallow wells, implied potential emissions. Flood irrigation experiments showed that 24.55% of dissolved CO2 and 36.81% of dissolved N2O in groundwater was degassed immediately (within 12 min of irrigation) to the atmosphere. Our study demonstrates that direct GHG emissions from groundwater used for agricultural irrigation in the Guanzhong Basin are potentially equivalent to about 2-4% of the GHG emissions from 3 years of fertilizer use on these farmlands, so further research should focus on optimizing irrigation strategies to mitigate GHG emissions.

A 3-year field study on lead immobilisation in paddy soil by a novel active silicate amendment.

Lead (Pb) is a toxic metal in industrial production, which can seriously threat to human health and food safety. Thus, it is particularly crucial to reduce the content of Pb in the environment. In this study, raw fly ash (FA) was used to synthesise a new active silicate materials (IM) employing the low-temperature-assisted alkali (NaOH) roasting approach. The IM was further synthesised to form zeolite-A (ZA) using the hydrothermal method. The physicochemical characteristics of IM and ZA amendments before and after Pb2+ adsorption were analysed using the Scanning electron microscope-Energy Dispersive Spectrometer (SEM-EDS), Fourier Transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) apparatuses. The results revealed the considerably change in the microstructure and functional groups of IM and ZA amendments, conducive to Pb2+ removal. Moreover, a 3-year field experiment revealed that the IM and ZA significantly improved the growth of rice and reduced available Pb by 21%-26.8% and 9.7%-16.9%, respectively. After 3 years of remediation, the Pb concentration of the rice grain reached the national edible standard (≤0.2 mg kg-1) of 0.171 mg kg-1 and 0.179 mg kg-1, respectively. Meanwhile, the concentration of acid-exchangeable Pb reduced, while those of reducible and residual fractions of Pb increased. There was no significant difference between the IM and ZA treatments. The potential mechanisms of remediation by the amendments were ion-exchange, complexation, precipitation, and electrostatic attraction. Overall, the results indicate that IM is suitable for the remediation of contaminated soil and promotes safe food production, and develops an environmentally friendly and cost-effective amendment for the remediation of polluted soil.

Effect and mechanisms of synthesis conditions on the cadmium adsorption capacity of modified fly ash.

In this study, modified coal fly ash (NMFA) was prepared by sodium hydroxide (NaOH) with low-temperature hydrothermal method. The differences of the ash to alkali mass ratio (5:3, 5:4, 5:5, 5:6), calcination temperature (100 â„ƒ, 200 â„ƒ, 300 â„ƒ), and calcination time (1 h, 3 h, 5 h) were investigated. The adsorption experiments obtained the optimal result with the ash to base ratio of 5:5, calcination temperature of 200 â„ƒ, and calcination time of 3 h, adsorbing 90.27 mg/g of Cd2+. The characterization results (SEM-EDS, FTIR, XRD, and XPS) also confirmed the effective adsorption of Cd2+ by NMFA. The functional groups of Si-O, Al-O, and Fe-O played an important role in Cd2+ removal. Meanwhile, the influences of dosage, different pH, and co-existing cations were also investigated. Quasi-secondary adsorption kinetics and Langmuir isotherm model were also referred to the Cd2+ adsorption by NMFA. Therefore, the good adsorption of NMFA-3 on Cd2+ provided new ideas for the safe utilization of fly ash and heavy metal purification in wastewater.

Effect of modified fly ash on environmental safety of two soils contaminated with cadmium and lead.

In this study, a low-temperature roasting and hydrothermal methods were used to modify the fly ash resulting in two new types of adsorption materials - modified fly ash (MFA) and artificial zeolite (ZE). These modified fly ashes, as well as a natural zeolite (ZO) were applied to two types of contaminated soils to explore their effects and mechanisms on the behavior of Cd and Pb through leaching column experiments. The bioavailable of Pb, Cd, pH, dissolved organic carbon (DOC), organic matter, as well as the microbial community changings were detected. The results showed that, 2% ZE has a significant stabilizing effect on Cd and the bioavailable fraction contents in Guanzhong (GZ) and Hunan (HN) soils decreased by 40.5% and 53.2%, respectively. However, for Pb, the 2% MFA showed a better result than that of ZE and ZO; the contents of bioavailable Pb in HN and GZ decreased by 48.3% and 30%, respectively. Furthermore, based on the Illumina NovaSep sequencing platform, 18 soil samples of GZ and HN were sequenced for microbial communities. As compared to the control blank(CK) treatment, the abundance of soil microbial communities was significantly improved in the amended soils.

Potential of using a new aluminosilicate amendment for the remediation of paddy soil co-contaminated with Cd and Pb.

Cadmium (Cd) and lead (Pb) are toxic heavy metals that impact human health and biodiversity. Removal of Cd/Pb from contaminated soils is a means for maintaining environmental sustainability and biodiversity. In this study, we applied a newly modified material fly ash (NA), zeolite (ZE), and fly ash (FA) to the paddy soils and evaluated the effects of Cd/Pb accumulation in rice via a one-year field experiment. The results showed that the application of NA and ZE enhanced the soil pH and nutrients to a large extent and reduced the availability of Cd/Pb in soil. The Cd and Pb concentrations in rice grains decreased by 32.8% and 62.9%, respectively, with the NA treatments. Similarly, the application of ZE reduced the Cd and Pb concentrations in rice grains by a factor of 27.9% and 63.5%, respectively, which indicates that the amendments can promote the transfer of Cd and Pb from acid-exchangeable fraction to oxidizable and residual fractions. The Cd/Pb showed a significant positive correlation to other metal ions and a negative correlation to the nutrients. Generally, the application of NA and ZE was effective in reducing Cd/Pb accumulation and improving rice yield. Moreover, the NA was more cost-effective than ZE. Hence, this study proves that NA may be a better amendment for remediation of Cd/Pb contaminated soils.

Potential of a novel modified gangue amendment to reduce cadmium uptake in lettuce (Lactuca sativa L.).

In this study, the modified gangue (GE) was prepared by calcination at lower temperatures using potassium hydroxide (KOH) as the activating agent. The field emission scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), and X-ray fluorescence (XRF) methods were employed to analyze the physicochemical characteristics of GE before and after the modification. Besides, the GE and commercial zeolite (ZE) were compared in the remediation of Cd-contaminated soil in field experiments. The results showed that both the GE and ZE had positive effects on the stabilization of Cd, decreasing the available Cd by 21.2-33.9% and 22.1-28.2%, respectively, while no significant difference was observed between the two amendments, indicating that the modification of GE was successful. Moreover, the application of GE decreased the Cd mobilization and uptake in lettuce shoot and root by 54.9-61.5% and 9.3-13.2%, respectively, and at the same time, the bio-available Cd decreased by 20.9-34.5%. Moreover, with the addition of GE, activities of urease and alkaline phosphatase increased in soil, while the peroxidase and superoxide dismutase activities were notably reduced in plants. Therefore, GE could be used as an effective amendment for the alleviation of Cd accumulation and toxicity, and thereby improve food safety.

Optimization of preparation technology for modified coal fly ash and its adsorption properties for Cd2.

This work focused on preparation a novel adsorbent from coal fly ash (CFA) and solid alkali (NaOH) by low temperature roasting method. The modification parameters (mass ratio, calcination time and temperature) were specifically studied and optimized. The adsorption experiment results indicated that, the adsorption amounts of Cd2+ were enhanced with the decreasing mass ratio of CFA and NaOH, and the adsorption amounts of Cd2+ were 32.44, 31.66, 38.5 and 79.85 mg/g at the mass ratio (CFA/NaOH) of 5:5, 5:6, 5:7 and 5:8, respectively. The higher modification temperature was not conducive to the removal of Cd2+, as the adsorption capacities of Cd2+ calculated were 62.42, 69.53 and 41.73 mg/g at the reaction temperature of 250, 300 and 400 ℃. Interestingly, the modification time slightly effects on the adsorption ability of materials. According to the results, the optimum modification condition for preparing adsorbents were CFA/NaOH mass ratio of 5:8 and calcined at 300 ℃ for 3 h. Moreover, the influence of pH, ionic strength and Glycine concentration on Cd2+ uptake were also investigated. The kinetic, adsorption isotherm and thermodynamics models were applied to investigate the adsorption mechanism, which indicated that the adsorption process was better fitted by Langmuir and pseudo-second-order models.

Potential of removing Cd(II) and Pb(II) from contaminated water using a newly modified fly ash.

Modified fly ash was prepared through low-temperature roasting method using NaOH as activator. The techniques of Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and the X-ray diffraction (XRD) were introduced to analyze the chemical and physical performance of samples, respectively. It was found that a significant improvements in activity and specific surface area of adsorbent. This work systematically reported the uptake performances of modified materials for single and two mixed toxic cations Pb(II) and Cd(II). The results unveiled that pseudo-second-order model was suitable to analyze the adsorption process. The adsorption process were better fitted by Langmuir model and the maximum uptake capacities were 126.55 and 56.31 mg g-1 for Pb(II) and Cd(II) in single system at 298 K, respectively. Additionally, in mixed solution, the maximum uptake capacity reduced to 120.48 and 36.10 mg g-1 under the same adsorption conditions. Competitive adsorption results demonstrated that adsorption ability was restricted by other metal ions, as while as, the binding affinity of two cations followed the order of Pb(II)>Cd(II). Meanwhile, the co-existed cations as Ca(II), Mg(II) Na(I) and K(I) had antagonistic effects on the uptake of Cd(II) and Pb(II). The results indicate that the modified fly ash was a low-cost and effective adsorbent for the cleaning up metal ions in wastewater, which has a promising application prospect.

Possibility of removing cadmium pollution from the environment using a newly synthesized material coal fly ash.

Coal fly ash (FA) is a solid waste produced in coal combustion. This study focused on the removal of Cd2+ from wastewater by a newly synthesized adsorbent material, the low-temperature and sodium hydroxide-modified fly ash (SHM-FA). The SEM and BET analyses of SHM-FA demonstrated that the adsorbent was porous and had a huge specific surface area. The XRF, XRD, FTIR and TGA characterization showed that SHM-FA has an amorphous structure and the Si-O and Al-O in the fly ash dissolved into the solution, which improved the adsorption capacity of Cd. The results indicated that SHM-FA has desired adsorption performance. The adsorption performance was significantly affected by the dosage, starting pH, Cd2+ initial concentrations, and temperature, as well as adsorption time. In the optimal conditions, the removal efficiency and adsorption capacity of Cd2+ by SHM-FA were 95.76% and 31.79 mg g-1, respectively. The experiment provided clearly explained adsorption kinetics and isotherms. And the results confirmed that the adsorption behavior was well described by the pseudo-second-order kinetic and Langmuir isotherm model, which means that the adsorption of Cd2+ was controlled by SHM-FA through surface reaction and external diffusion process. In addition, the recycling of SHM-FA for reuse after Cd2+ adsorption showed high removal efficiency up to six times of use. Therefore, it can be concluded that SHM-FA is a low-cost adsorbent for Cd2+ removal from wastewater.

Potential of enhancing the phytoremediation efficiency of Solanum nigrum L. by earthworms.

Contamination of the soil by Cadmium (Cd) is emerged as a critical environmental problem in China due to current urbanization and industrial activities that hinder the sustainable future development of agriculture. In this study, a system combined by earthworm and Solanum nigrum L. (S. nigurm) was designed for remediation of Cadmium from contaminated soils. The present study revealed that application of earthworm enhanced the biomass of S. nigrum by 61.71%, maxim; the Cd concentrations in the aboveground part of S. nigrum enhanced 35.8% when 50 g earthworm was added into each pot; the addition of earthworm also have some effect on the bio-concentration factor (BF) of S. nigrum while no effect was detected on the bio-transfer factor (TF). In addition, considering the accumulation of Cd by earthworm, the total amount of Cd extracted by the combined system enhanced 57.7% at least and 264.6% at the most, compared to the Cd extraction amount of S. nigrum alone. Generally, according to this study, the earthworm-S. nigrum system has the potential to be used for the remediation of Cd contaminated soils.