Goethite modified biochar simultaneously mitigates the arsenic and cadmium accumulation in paddy rice (Oryza sativa) L.

Cadmium (Cd) and arsenic (As) contamination of paddy soils is a serious global issue because of the opposite geochemical behavior of Cd and As in paddy soils. Rice plant (Oryza sativa L.) cultivation in Cd- and As- contaminated paddy soil is regarded as one of the main dietary cause of Cd and As entry in human beings. This study aimed to determine the impact of goethite-modified biochar (GB) on bioavailability of both Cd and As in Cd- and As- polluted paddy soil. Contrary to control and biochar (BC) amendments, the application of GB amendments significantly impeded the accumulation of both Cd and As in rice plants. The results confirmed an obvious reduction in Cd and As content of rice grains by 85% and 77%, respectively after soil supplementation with GB 2% amendment. BC 3% application minimized the Cd uptake by 59% in the rice grains as compared to the control but exhibited a little impact on As accumulation in rice grains. Sequential extraction results displayed an increase in immobile Cd and As fractions of the soil by decreasing the bioavailable fractions of both elements after GB treatments. Fe-plaque formation on the root surfaces was significantly variable (P Ë‚ 0.05) among all the amendments. GB 2% treatment significantly increased the Fe content (10 g kg-1) of root Fe-plaque by 48%, which ultimately enhanced the sequestration of Cd and As by Fe-plaque and minimized the transport of Cd and As in rice plants. Moreover, GB treatments significantly changed the relative abundance of the microbial community in the rice rhizosphere and minimized the metal(loid)s mobility in the soil. The relative abundance of Acidobacteria, Firmicutes and Verrucomicrobia increased with GB 2% treatment while those of Bacteroidetes and Choloroflexi decreased. Our findings confirmed improvement in the rice grains quality regarding enhanced amino acid contents with GB application. Overall, the results of this study demonstrated that GB amendment simultaneously alleviated the Cd and As concentrations in edible parts of rice plant and provided a new valuable method to protect the public health by effectively remediating the co-occurrence of Cd and As in paddy soils.

Effect of phytic acid and morphology on Fe (oxyhydr)oxide transport under saturated flow condition.

Phytic acid (myo-inositol hexaphosphate, IHP) is a dominant form of organic phosphate (OP) in organic carbon-rich surface soil. The IHP impact on Fe (oxyhydr)oxide transport is critical for iron and phosphorus (bio)geochemical processes in iron and phosphorus rich soil and subsurface systems. Three typical Fe (oxyhydr)oxides (ferrihydrite, hematite, and goethite) were studied in this research. The effects of IHP and morphology on Fe (oxyhydr)oxide transport and IHP cotransport had been investigated using saturated sand columns. The results showed that IHP significantly enhanced the mobility of Fe (oxyhydr)oxide by 30-90% due to the stronger electrostatic repulsion. At low IHP concentration (< 50 µM IHP), the rod-like goethite and goethite-facilitated IHP showed high mobility due to their orientation and motion along the water flow, which is 70% faster than ferrihydrite and hematite at pH 5 and 90% faster at pH 10. The mobility of amorphous ferrihydrite was slowest among three selected iron oxides (< 37% at pH 5 and < 72% at pH 10). At high IHP concentration (> 50 µM IHP), the surface precipitation might have occurred on ferrihydrite because of its poorly ordered crystallinity, contributing to its less negatively charged surface and weak transport. The new insight provided in this study is essential for evaluating the fate and transport behavior of iron and iron-facilitate OP in soil rich in iron and OP.

Critical insight and indication on particle size effects towards uranium release from uranium mill tailings: Geochemical and mineralogical aspects.

Uranium (U) is both chemically toxic and radioactive. Uranium mill tailings (UMTs) are one of the most important sources of U contamination in the environment, wherein the mechanisms that control U release from UMTs with different granularities have not yet been well understood. Herein, the release behaviours and underlying release mechanisms of U from UMTs with five different particle size fractions (<0.45, 0.45-0.9, 0.9-2, 2-6 and 6-10 mm) were studied with a well-defined leaching test (ANS 16.1) combined with geochemical and mineralogical characterizations. The results showed that the most remarkable U release unexpectedly emerged from UMT2-6 mm; in contrast, the smallest particle size UMT<0.45 mm contributed to the least U release. The predominant mechanism of U release from UMT2-6 mm was the oxidative dissolution of U-bearing sulfides, while abundant gypsum present in UMT<0.45 mm inhibited U release. The study highlights the importance of combined geochemical and mineralogical investigation when performing leaching tests of mineral-containing hazardous materials such as UMTs with consideration of particle size effects. The findings also indicate that elevating the content of gypsum and avoiding the oxidation of sulfides can effectively help immobilize and minimize the residual U release from the UMTs.

Goethite-modified biochar ameliorates the growth of rice (Oryza sativa L.) plants by suppressing Cd and As-induced oxidative stress in Cd and As co-contaminated paddy soil.

Co-contamination of soils with cadmium (Cd) and arsenic (As) in rice growing areas is a serious threat to environment and human health. Increase in soil Cd and As levels curtail the growth and development of rice plants by causing oxidative stress and reduction in photosynthetic activity. Therefore, it is necessary to formulate and evaluate different strategies for minimizing the Cd and As uptake in rice plant. We modified biochar (BC) with goethite and assessed the effects of goethite-modified biochar (GB) application on mitigating Cd and As stress in rice plant. Although BC supply to rice plants enhanced their performance in contaminated soil but application of different GB levels i.e.1.5% GB to the soil resulted in prominent improvements in physiological and biochemical attributes of rice plants grown in Cd and As co-contaminated paddy soil. It was observed that soil amendment with GB increased the plant growth, biomass, photosynthetic pigments, gas exchange attribute of rice plant and suppressed the oxidative stress in rice leaves and roots by increased antioxidant enzymes activities. Supplementing the soil with 1.5% GB incremented the iron plaque (Fe-plaque) formation and enhanced the Cd and As sequestration by Fe-plaque. Application of GB (1.5%) significantly improved the Fe content of Fe-plaque by 68.7%. Maximum Cd (1.57 mg kg-1) and As (0.85 mg kg-1) sequestration by Fe-plaque was observed with 1.5% GB treatment. Compared to the control, 1.5% GB treatment application prominently reduced the Cd content in the rice roots and shoots by 42.9%, and 56.7%, respectively and As content in the rice roots and shoots declined by 32.2%, 46.6%, respectively, compared to the control. These findings demonstrate that amending the soil with 1.5% GB can be a potential remediation strategy for checking Cd and As accumulation, reducing oxidative stress and increasing the growth of rice plant.

Goethite-modified biochar restricts the mobility and transfer of cadmium in soil-rice system.

Cadmium (Cd) contamination of paddy soils has raised serious concerns for food safety and security. Remediation and management of Cd contaminated soil with biochar (BC) and modified biochar is a cost-effective method and has gained due attention in recent years. Goethite-modified biochar (GB) can combine the beneficial effects of BC and iron (Fe) for remediation of Cd contaminated soil. We probed the impact of different BC and GB amendments on Cd mobility and transfer in the soil-rice system. Both BC and GB effectively reduced Cd mobility and availability in the rhizosphere and improved the key growth attributes of rice. Although BC supply to rice plants enhanced their performance in contaminated soil but application of 1.5% GB to the soil resulted in prominent improvements in physiological and biochemical attributes of rice plants grown in Cd contaminated soil. Sequential extraction results depicted that BC and GB differentially enhanced the conversion of exchangeable Cd fractions to non-exchangeable Cd fractions thus restricted the Cd mobility and transfer in soil. Furthermore, supplementing the soil with 1.5% GB incremented the formation of iron plaque (Fe plaque) and boosted the Cd sequestration by Fe plaque. Increase in shoot and root biomass of rice plants after GB treatments positively correlates with incremented chlorophyll contents and gas exchange attributes. Additionally, the oxidative stress damage in rice plants was comparatively reduced under GB application. These findings demonstrate that amending the soil with 1.5% GB can be a potential remediation method to minimize Cd accumulation in paddy rice and thereby can protect human beings from Cd exposure.

Spatial patterns in soil physicochemical and microbiological properties in a grassland adjacent to a newly built lake.

Soil water content (SWC) is an important determinant for nutrient cycling and microorganism activity in the grassland ecosystem. Lakes have a positive effect on the water supply of the neighboring ecosystem. However, information evaluating whether newly built lakes improve the physiochemical properties and microorganism activity of adjacent grassland soil is rare. A 15-hectare artificial lake with a 2 m depth was built on grazed grassland to determine whether the change of soil physiochemical properties and microorganism activity of the adjacent grassland depended on the distance from the lake. SWC and total nitrogen (TN) were greater within 150 m of the lake than at distances over 150 m from the lake. The total organic carbon (TOC) increased first at 100-150 m from the lake and then decreased. The soil microbial biomass and the bacterial and fungal contents increased with increasing years after the construction of the lake. Gram-negative bacteria and methanotrophic bacteria were greater within a 30 m distance of the lake. Over 60 m away from the lake, Actinobacteria, gram-positive bacteria, and anaerobic bacteria showed higher abundances. In the area near the lake (<250 m distance), microorganisms were strongly correlated with SWC, EC, TN, and TOC and greatly correlated with the changes of total phosphorous (TP) and pH when the distance from the lake was over 250 m. The results indicated that the newly built lake could be a driving factor for improving the physiochemical properties and microorganism activity of adjacent grassland soil within a certain range.

Graphene oxide-facilitated uranium transport and release in saturated medium: Effect of ionic strength and medium structure.

Natural subsurface environment is a complex heterogeneous system. To investigate the effect of ionic strength (IS) and heterogeneity on the transport and remobilization of graphene oxide (GO)-facilitated uranium (U(VI)) in saturated porous media, column experiments were performed by the injection of U(VI) alone and U(VI)+GO mixtures into homogeneous and heterogeneous porous media under low and high ionic strength (1 and 50 mM) conditions, and then the columns were successively flushed with background solution and DI water. Results showed that when U(VI) only was introduced into the columns, IS had little effect on the migration of U(VI) alone in both media and the presence of preferential flow in heterogeneous media slightly enhanced the mobility of U(VI). As U(VI)+GO mixtures were injected into the columns, GO showed strong mobility at low IS and high released peak at high IS. The appearance of GO significantly enhanced U(VI) transport in both media. Under low IS condition, the mobility of U(VI) was significantly enhanced at the injection phase, and the medium heterogeneity further promoted the amount of GO-sorbed U(VI) transport. At high IS, less GO-sorbed U(VI) was observed during injection phase, and a large amount of retained GO-sorbed U(VI) were released with GO remobilization during water flushing phase, and the release showed the longer-tailing phenomenon and the release amount was more pronounced in heterogeneous media. The findings in this study showed that the coupled effect of solution chemistry and media heterogeneity played important roles on GO-facilitated U(VI) transport and release in soil and groundwater system.

Mechanism of uranium release from uranium mill tailings under long-term exposure to simulated acid rain: Geochemical evidence and environmental implication.

To date, there is not sufficient knowledge to fully understand the occurrence, transport and fate of residual uranium (U) from uranium mill tailings (UMT). Herein this study investigated different U release behaviors from natural UMT (without grinding) under four simulated acid rain (pH = 2.0-5.0) compared with controlled scenario (pH = 6.0) for 25 weeks. The results showed that the most notable U release was observed from UMTpH2.0, followed by UMTpH3.0 whereas a nonlinear relationship between pH and U release was observed from UMTpH4.0-6.0. The divergence of U release behaviors was attributed to the presence of minerals such as calcite and clinochlore. Autunite, a secondary mineral formed after leaching, might regulate U release in UMTpH3.0-6.0. Fick theory model revealed the shift of U release mechanism from surface dissolution to diffusion transport for UMTpH2.0, UMTpH3.0 and UMTpH5.0 at varied stage, whereas UMTpH4.0 and UMTpH6.0 displayed univocal dissolution and diffusion mechanism, respectively. This study highlights the necessity of performing long-term leaching tests to detect the "shift event" of leaching kinetics and to better understand the mechanism of U release influenced by mineralogy of the natural UMT under simulated acid rain conditions, which is conducive to developing UMT management strategies to minimize the risk of U release and exposure.

Uranium (VI) transport in saturated heterogeneous media: Influence of kaolinite and humic acid.

Natural aquifers typically exhibit a variety of structural heterogeneities. However, the effect of mineral colloids and natural organic matter on the transport behavior of uranium (U) in saturated heterogeneous media are not totally understood. In this study, heterogeneous column experiments were conducted, and the constructed columns contained a fast-flow domain (FFD) and a slow-flow domain (SFD). The effect of kaolinite, humic acid (HA), and kaolinite/HA mixture on U(VI) retention and release in saturated heterogeneous media was examined. Media heterogeneity significantly influenced U fate and transport behavior in saturated subsurface environment. The presence of kaolinite, HA, and kaolinite/HA enhanced the mobility of U in heterogeneous media, and the mobility of U was the highest in the presence of kaolinite/HA and the lowest in the presence of kaolinite. In the presence of kaolinite, there was no difference in the amount of U released from the FFD and SFD. However, in the presence of HA and kaolinite/HA, a higher amount of U was released from the FFD. The findings in this study showed that medium structure and mineral colloids, as well as natural organic matter in the aqueous phase had significant effects on U transport and fate in subsurface environment.

Investigation of U(VI) adsorption in quartz-chlorite mineral mixtures.

A batch and cryogenic laser-induced time-resolved luminescence spectroscopy investigation of U(VI) adsorbed on quartz-chlorite mixtures with variable mass ratios have been performed under field-relevant uranium concentrations (5×10(-7) M and 5×10(-6) M) in pH 8.1 synthetic groundwater. The U(VI) adsorption Kd values steadily increased as the mass fraction of chlorite increased, indicating preferential sorption to chlorite. For all mineral mixtures, U(VI) adsorption Kd values were lower than that calculated from the assumption of component additivity possibly caused by surface modifications stemming from chlorite dissolution; The largest deviation occurred when the mass fractions of the two minerals were equal. U(VI) adsorbed on quartz and chlorite displayed characteristic individual luminescence spectra that were not affected by mineral mixing. The spectra of U(VI) adsorbed within the mixtures could be simulated by one surface U(VI) species on quartz and two on chlorite. The luminescence intensity decreased in a nonlinear manner as the adsorbed U(VI) concentration increased with increasing chlorite mass fraction-likely due to ill-defined luminescence quenching by both structural Fe/Cr in chlorite, and trace amounts of solubilized and reprecipitated Fe/Cr in the aqueous phase. However, the fractional spectral intensities of U(VI) adsorbed on quartz and chlorite followed the same trend of fractional adsorbed U(VI) concentration in each mineral phase with approximate linear correlations, offering a method to estimate of U(VI) concentration distribution between the mineral components with luminescence spectroscopy.

Effect of subgrid heterogeneity on scaling geochemical and biogeochemical reactions: a case of U(VI) desorption.

The effect of subgrid heterogeneity in sediment properties on the rate of uranyl[U(VI)] desorption was investigated using a sediment collected from the U.S. Department of Energy Hanford site. The sediment was sieved into 7 grain size fractions that each exhibited different U(VI) desorption properties. Six columns were assembled using the sediment with its grain size fractions arranged in different spatial configurations to mimic subgrid heterogeneity in reactive transport properties. The apparent rate of U(VI) desorption varied significantly in the columns. Those columns with sediment structures leading to preferential transport had much lower rates of U(VI) desorption than those with relatively homogeneous transport. Modeling analysis indicated that the U(VI) desorption model and parameters characterized from well-mixed reactors significantly overpredicted the measured U(VI) desorption in the columns with preferential transport. A dual domain model, which operationally separates reactive transport properties into two subgrid domains, improved the predictions significantly. A similar effect of subgrid heterogeneity, albeit to a lesser degree, was observed for denitrification, which also occurred in the columns. The results imply that subgrid heterogeneity is an important consideration in extrapolating reaction rates from the laboratory to field.

Effect of grain size on uranium(VI) surface complexation kinetics and adsorption additivity.

The contribution of variable grain sizes to uranium adsorption/desorption was studied using a sediment from the US DOE Hanford site. The sediment was wet sieved into four size fractions: coarse sand (1-2 mm), medium sand (0.2-1 mm), fine sand (0.053-0.2 mm), and clay/silt fraction (<0.053 mm). For each size fraction and their composite (sediment), batch and flow-cell experiments were performed to determine uranium adsorption isotherms and kinetic uranium adsorption and subsequent desorption. The results showed that uranium adsorption isotherms and adsorption/desorption kinetics were size specific, reflecting the effects of size-specific adsorption site concentration and kinetic rate constants. The larger-size fraction had a larger mass percentage in the sediment but with a smaller adsorption site concentration and generally a slower uranium adsorption/desorption rate. The same equilibrium surface complexation reaction and reaction constant could describe uranium adsorption isotherms for all size fractions and the composite after accounting for the effect of adsorption site concentration. Mass-weighted, linear additivity was observed for both uranium adsorption isotherms and adsorption/desorption kinetics in the composite. One important implication of this study is that grain-size distribution may be used to estimate uranium adsorption site and adsorption/desorption kinetic rates in heterogeneous sediments from a common location.