Aging properties and cadmium remediation mechanism of biochar in sediment from phosphorus-rich water.

Cadmium (Cd) is the main heavy metal pollutant in sediments from East China. The biochar-sediment nexus can provide carbon sequestration and pollution control. In this work, an in situ study was conducted to investigate the long-term effects and control mechanism of biochar and the effect of biochar aging on Cd stabilization in overlying water-pore water-sediment. The Cd2+ concentration in the overlying water was positively correlated with total nitrogen (0.960, P < 0.05), total organic carbon (0.983, P < 0.05), and total phosphorus (0.993, P < 0.01) in pore water. Biochar stabilized Cd2+ by increasing the pH and oxidation-reduction potential of the sediment environment and promoting the formation of Cd1.25Ca0.75(P2O7) on the biochar surface in sediment from phosphorus-rich water. These changes were closely related to the Brunauer-Emmett-Teller surface area and average pore size of the biochar. Within 60 days, the biochar in the sediment underwent aging, which was closely related to the preparation temperature of the biochar. The organic composition of biochar prepared at a low temperature (≤ 300 °C) and the surface structure of biochar prepared at a high temperature (≥ 500 °C) were altered. The biochar parameter changes were in the order of pore volume > Brunauer-Emmett-Teller surface area > pore size. Our results show that biochar modification can enhance the remediation capacity of biochar, but may be unfavorable to biochar anti-aging. This knowledge will support policymakers and researchers when exploring long-term biochar use in contamination control and strengthen future research.

Multi-media distribution and risk assessment of per- and polyfluoroalkyl substances in the Huai River Basin, China.

The widespread existence, environmental persistence, and risks of per- and polyfluoroalkyl substances (PFASs) have attracted widespread attention. Herein, the distribution and risk assessment of PFASs were investigated from the Huai River Basin. The ranges in different media were 29.83-217.96 (average of 75.82 ± 35.64 ng/L) in water, 0.17-9.55 ng/g (2.56 ± 2.83 ng/g) in sediments, and 0.21-9.76 ng/g (3.43 ± 3.07 ng/g) in biota. Perfluoropentanoic acid (PFPeA) was the most prevalent PFAS in surface water, followed by perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA), accounted for 42.62 %, 22.23 % and 17.72 % of the total concentrations of the PFASs analyzed, respectively. PFBA was dominant in sediments, accounting for 60.37 % of the total concentrations of the PFASs analyzed. Perfluorooctane sulfonate (PFOS) was the main pollutant in biota, and the highest concentration (5.09 ng/g) was found in Channa argus. Considering the measured concentrations in water, sediments and biota, the sediment-water partition coefficients (log Kd) and bioaccumulation factors (BAF) of PFASs were determined. The log Kd of the PFASs differed among those with a different carbon chain length, C7-C11 PFASs were more likely to be adsorbed onto sediments as the carbon chain length increases, and PFUnDA and PFDA showed the higher BAF value in Channa argus. PFASs in the Huai River Basin posed an acceptable ecological risk, and long-chain PFAS contamination provided green algae with a higher potential ecological risk. Compared to drinking water, aquatic products constituted a higher PFASs threat to human health, especially for children. The highest HQ was found in PFOS, with an HQmax of 0.97-4.32. Residents in the Huai River Basin should reduce their intake of Channa argus, Coilia nasus, and Carassius auratus, children aged 2 to 4 are limited to consuming no more than 6.9 g/d, 9.7 g/d, and 16.6 g/d, respectively.

Effect of river-lake connectivity on ecological stoichiometry of lake and carbon storage status in Eastern Plain, China.

C, N, and P in lake sediment are the basis of material and energy cycle, reflecting the economic development, ecological function, and environmental effect. Current research on the effect of lake eutrophication on carbon storage and the river-lake connectivity on nutrient diffusion is lack. This work investigated the accumulation, distribution, correlations, and stoichiometric ratios of C, N, and P of 82 lakes (≥ 10 km2) in Eastern China, analyzed the nutrient limitation, sediment carbon sink, and effect of river-lake connectivity, and discussed the relationships between eutrophication and sediment carbon storage. The average concentrations and ranges of total C, N, and P in lake sediments were (23.26 mg/g, 0.08-153.45 mg/g), (2.32 mg/g, 0.29-14.17 mg/g), and (0.86 mg/g, 0.23-2.64 mg/g), respectively. The ecological stoichiometry of C: N: P in lake sediments was 32: 3.2: 1. P can be easily accumulated in lakes connected from the Yangtze River, while C and N can be easily accumulated in disconnected lakes. The soil-water erosion in runoff is an important factor for P diffusion. The C/N and C/N/P weren't affected by the river-lake connectivity but depended on the plant type. The Eastern Plain Lake Region of China is C and N co-depletion, and P enrichment. The lake eutrophication leading to algal bloom is unfavorable to the goal of carbon storage and carbon neutrality. Outcome of this study will provide a significant reference and strategies for carbon sequestration research, eco-environmental protection, and watershed nutrient management.

Research on the geochemical background values and evolution rules of lake sediments for heavy metals and nutrients in the Eastern China Plain from 1937 to 2017.

For the first time, background quality guidelines have been developed for lake sediments along the Yangtze River. Evolution Rules of watershed environment in Eastern China were analyzed in 1937-2017. These methods of 137Cs and 210Pb radionuclide, 75% cumulative frequency, and background method were applied to calculate the sediment geochemical backgrounds (GB). The average GB values of Cu, Zn, Cd, Pb, Cr, total carbon (TC), total nitrogen (TN) and total phosphorus (TP) are 45.14 mg/kg, 86.99 mg/kg, 0.29 mg/kg, 33.71 mg/kg, 110.90 mg/kg, 17.20 mg/g, 1.60 mg/g, and 665.78 mg/kg, respectively. The radionuclide methods indicated that the sediment rate of 34 cm corresponding to 1963 is 0.63 cm yr-1. The risk and accumulation of the sediment metals and nutrients in Yangtze Plain were uncontaminated levels before 1960, raised since 1980, and increased significantly in 2000. The Cd, TC, and TN in lake sediment were at low to moderate pollution, and few lakes are at high pollution. Sediment background values of the plain are different from soil background values in China and Consensus-Based Sediment Quality Guidelines in Europe/America. Results of sediment quality guidelines provide an important guidance for pollution prevention, environmental management, and risk assessment, especially the formulation of environmental laws.

Effect of river-lake connectivity on heavy metal diffusion and source identification of heavy metals in the middle and lower reaches of the Yangtze River.

Metal pollution poses a significant threat to ecological security and human health. Current research on the causes, sources and distribution of metal pollution in the Yangtze River plain is lacking. This study investigated the accumulation, risk, distribution, and sources of heavy metals in 62 lakes along the Yangtze River, and analyzed the relationship between river-lake connectivity, economic structure, population and metal diffusion. The mean concentrations of Cr, Cu, Hg, Zn, Cd, Pb and As in the surface sediments of these lakes were 90.8, 60.1, 0.06, 102, 0.89, 42.7, and 6.01 mg/kg, respectively. Most (99%) of the lake sediments were contaminated with Cd, and the lakes in the middle reach and southern bank of the Yangtze River had a higher ecological risk. Cr originated from the natural environment, whereas Zn, Cu, Pb, Cd and As were affected by human activities. The lakes disconnected from the Yangtze River had higher concentrations of Cu, Zn, Pb and As, while the lakes connected to the river had higher concentrations of Cd and Cr. This comprehensive analysis determined the pollution characteristics of heavy metals, illustrated the causes of non-point pollution in the Yangtze River plain, and showed that soil-water erosion is important in metal diffusion.

Simultaneous reduction of arsenic and cadmium bioavailability in agriculture soil and their accumulation in Brassica chinensis L. by using minerals.

In situ immobilization of heavy metal cations in contaminated soil using natural minerals is an attractive remediation technique. However, little research has focused on the remediation of arsenic (As) and cadmium (Cd) co-contaminated. In this work, three different crystal structures and chemical compositions minerals, zeolite; bentonite; and dolomite, were applied to simultaneously reduce the uptake of As and Cd in Brassica chinensis L., and the mechanism on reducing As and Cd bioavailability in soil were also investigated. The results showed that the three minerals decreased the bioavailability of As and Cd and restrained their uptake by Brassica chinensis L. with the order followed bentonite > zeolite > dolomite. Particularly, bentonite decreased the exchangeable As and Cd by 4.05% and 32.5% and the concentrations of As and Cd in shoots of Brassica chinensis L. by 36.2% and 64.6%, as compared with the controls. Moreover, with the addition of minerals increased, the dry biomass of Brassica chinensis L. and the rhizosphere microbial functional diversity increased significantly, and the highest biomass increased by 289% at 4.0% addition of bentonite. Correlation analysis indicated that the uptake of As and Cd was positive with the available Cd and As in soil, and was negative with soil pH and available N. Furthermore, the Scanning Electron Microscopy-Energy Dispersive Spectroscopy and Fourier Transform Infrared Spectroscopy analysis illustrated the interaction between minerals and Cd mainly involved ion-exchange and adsorption, while As was mainly immobilized by calcium and magnesium through forming precipitation. In conclusion, this present study implied that the bentonite can be recommended as the more effective amendment to immobilize metal (loid)s in soil and thereby reduce the exposure risk of metal (loid)s associated with grains consumption.

Highly efficient remediation of groundwater co-contaminated with Cr(VI) and nitrate by using nano-Fe/Pd bimetal-loaded zeolite: Process product and interaction mechanism.

Hexavalent chromium and nitrate co-contaminated groundwater remediation are attracting extensive attention worldwide. However, the transformation pathways of chromium and nitrate and the interplay mechanism between them remain unclear. In this work, zeolite-supported nanoscale zero-valent iron/palladium (Z-Fe/Pd) was synthesized and used for the first time to simultaneously remediate Cr(VI) and nitrate. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that nanoscale zero-valent iron/palladium was successfully loaded onto zeolite and it exhibited good dispersibility and oxidation resistance. Results of batch experiments showed that the Cr(VI) and nitrate removal efficiencies decreased from 95.5% to 91.5% to 45% and 73%, respectively, with the initial solution pH increasing from 3.0 to 8.0. The removal rates and efficiencies of Cr(VI) and nitrate under anoxic conditions were higher than those under open atmosphere because the dissolved oxygen diminished the electron selectivity toward the target pollutants. Moreover, the presence of Cr(VI) inhibited nitrate reduction by forming Fe(III)-Cr(III) hydroxide to impede electron transfer. Cr(VI) removal was promoted by nitrate, within limits, by balancing the consumption and generation rate of Fe3O4, which enhanced electron migration from the Fe(0) core to the external surface. The removal capacities of Cr(VI) and nitrate reached 121 and 95.5 mg g-1, respectively, which were superior to the removal capacities of similar materials. Results of product identification, XRD, and XPS analyses of spent Z-Fe/Pd indicated that the reduction of Cr(VI) was accompanied by adsorption and co-precipitation, whereas the reduction of nitrate was catalyzed by the synergism of Fe(0) and Pd(0). An alternative to the simultaneous remediation of Cr(VI) and nitrate from groundwater under anoxic conditions is provided.

The influence of corncob-based biochar on remediation of arsenic and cadmium in yellow soil and cinnamon soil.

Biochar plays a significant role in soil remediation. However, the simultaneous immobilization mechanism and relationship of biochar to cations and anions have never been clear. We designed a batch incubation experiment to investigate the impact of corncob-based biochars to cadmium (Cd) and arsenic (As) contaminations in yellow soil and cinnamon soil, and analyze the relationships among biochars physicochemical characteristics (surface area: SA, total pore volume: TV, average pore size: AV and the C/O rate), soil properties, metals immobilization and microbial diversity indices. Results showed that the modified biochars (inorganic-modified biochar: BCTD) had a good effect on heavy metals immobilization and transformed acid extractable and reducible fraction into the residual fraction. Total nitrogen, organic matter and available potassium increased in both soils after biochar application. The principal component analysis presented that the smaller C/O rate was favorable to As stabilization; the SA and TV of biochar were negatively correlated with the leaching concentration of Cd. The larger surface area, higher porosity and organic matters of biochar were more beneficial to soil microbial diversity. This work not only can demonstrate remediation mechanisms of heavy metals contaminated soil by biochars, but also gain an application of biochars technology in the recycling and reutilize of agricultural waste, and provide a clear strategy for heavy metals contaminated soil, especially As and Cd.

Efficient simultaneous removal of cadmium and arsenic in aqueous solution by titanium-modified ultrasonic biochar.

Simultaneous removal of cations and anions in wastewater has always been a great concerned environmental problem. In this study, a friendly and inexpensive biosorbent to simultaneously remove Cd(II) and As(V) from aqueous solution was synthesized by ultrasonic biochar and nanoscale TiO2 (TD), and the obtained sorbent was named as BCTD. The maximum sorption capacities of Cd (72.62 mg/g) and As (118.06 mg/g) were much higher than that of other carbon-materials. Both experiments showed that the Cd(II) and As(V) adsorption capacity was above 70% at pH = 5. The Cd(II) and As(V) adsorption on BCTD had a competitive effect in binary metal solutions at above 100 mg/L. The BET, SEM-EDS, FTIR and XPS analyses proved that ultrasonically reacting enhanced the surface area and pore volume of biochar and TD was supported on the biochar surface and inner pores successfully, and the dominant sorption mechanism by BCTD was the ion exchange and complexation.

[Effects of Bentonite on Chemical Forms and Bioavailability of Heavy Metals in Different Types of Farmland Soils].

A pot experiment was conducted to evaluate the effects of bentonite on the physicochemical properties of soil; chemical forms of Cd, As, V, and Cr; pakchoi (Brassica chinensis L.) growth; metal uptake; and rhizosphere microbial community in three different types of farmland soils. The results showed that bentonite decreased the exchangeable Cd in the sequence of Yellow earths (Gy, 19.44%) > Yellow-cinnamon soils (Sy, 13.85%) > Fluvo-aquic soils (Bf, 5.03%), and the content of Cd in shoots of pakchoi declined in the sequence of Gy (34.81%) > Bf (23.91%) > Sy (11.11%), compared with the controls. Compared with the controls, the exchangeable As in Bf and Sy decreased by 4.53% and 25.16%, respectively, while the exchangeable As in Gy increased by 0.57%. The exchangeable Cr was increased in the sequence of Sy (31.30%) > Gy (2.91%) > Bf (0.58%). The residual As, V, and Cr increased (except for Cr in Sy), and their uptake was also reduced in different degrees. The addition of bentonite significantly promoted the growth of pakchoi in the three soil types, especially in Bf. pakchoi biomass, root surface area, and number of root tips increased by 147.55%, 80.71%, and 124.31%, respectively, in Bf, compared with the control. In addition, bentonite reduced the content of available nitrogen, phosphorus, and organic matter; increased the content of available potassium; and increased the diversity of rhizosphere microbial community in all three soils. Therefore, bentonite could be highly recommended as a safe stabilizer in these three types of soil.

A novel modification of lignin on corncob-based biochar to enhance removal of cadmium from water.

In order to improve the adsorption capacities of corncob-based biochars for heavy metal, the different pyrolysis temperature (350 °C, 450 °C and 550 °C) of corncob-based biochars were modified with the acrylonitrile, and adsorption capacities of Cadmium from solution by biochars were studied. The results showed that only at 350 °C the biochar can be successfully modified. The Cd adsorption capacity (85.65 mg/g) by the biosorbent was higher than other methods of modifying biochars previously reported. SEM-EDS and FTIR confirmed that the CN group was grafted on the biochar at low pyrolysis temperature. Batch adsorption experiment including pH-dependence, adsorption kinetics, and isotherms and XPS results showed that the removal mechanism of Cd(II) by the modified biochar was ion exchange and adsorption-complexation. This research not only obtained a novel method to modify biochar but also furthered research into the lignin of biochar composition, and provided an efficient sorbent for heavy metal.