Atomically Dispersed Manganese on Biochar Derived from a Hyperaccumulator for Photocatalysis in Organic Pollution Remediation.

Phytoremediation is a potentially cost-effective and environmentally friendly remediation method for environmental pollution. However, the safe treatment and resource utilization of harvested biomass has become a limitation in practical applications. To address this, a novel manganese-carbon-based single-atom catalyst (SAC) method has been developed based on the pyrolysis of a manganese hyperaccumulator, Phytolacca americana. In this method, manganese atoms are dispersed atomically in the carbon matrix and coordinate with N atoms to form a Mn-N4 structure. The SAC developed exhibited a high photooxidation efficiency and excellent stability during the degradation of a common organic pollutant, rhodamine B. The Mn-N4 site was the active center in the transformation of photoelectrons via the transfer of photoelectrons between adsorbed O2 and Mn to produce reactive oxygen species, identified by in situ X-ray absorption fine structure spectroscopy and density functional theory calculations. This work demonstrates an approach that increases potential utilization of biomass during phytoremediation and provides a promising design strategy to synthesize cost-effective SACs for environmental applications.

A meta-analysis about the accumulation of heavy metals uptake by Sedum alfredii and Sedum plumbizincicola in contaminated soil.

Sedum alfredii and Sedum plumbizincicola typically have high heavy metal (such as Zn and Cd) accumulation capacities with fast growth rates and relatively high Pb tolerance in contaminated soils. We compared the accumulation characteristics of heavy metals in Sedum species through meta-analysis. Furthermore, we analyzed the effects of soil organic matter (SOM) and soil pH on Cd, Pb and Zn accumulation by S. alfredii and S. plumbizincicola and the correlation between various metals. Results showed that the accumulations of Cd and Zn in shoots were higher than that of roots, but Pb accumulated in roots more than shoots. Moreover, there is a significant positive correlation between the accumulation of Zn and Cd in shoots. We found that the heavy metal accumulation rate in shoots was higher with lower soil pH. Sedum species had the highest Cd adsorption capacity in 20-30 g/kg SOM and the highest Zn adsorption capacity in SOM less than 20 g/kg. The accumulation rate of Cd in shoots of S. plumbizincicola was increased with exposure time, while the accumulation rate of Zn was slightly decreased.

S. alfredii and S. plumbizincicola are two common Cd and Zn hyperaccumulators. We systematically compared the accumulation characteristics of heavy metals in Sedum plants and the effects of soil organic matter and pH on the accumulation of Cd, Pb and Zn in S. alfredii and S. plumbizincicola through meta-analysis. This provides certain theoretical knowledge for the application of sedum plants to the phytoremediation of heavy metal contaminated soils.

Effects of various warming patterns on Cd transfer in soil-rice systems under Free Air Temperature Increase (FATI) conditions.

Global warming has become an important research topic in different disciplines around the world, especially in the fields of environment quality and food security. As a potential problem in soil environments, cadmium (Cd) contamination of rice under global warming conditions has not been thoroughly investigated. In this study, the fate of Cd in soil-rice systems under various warming patterns was studied via pot experiments under Free Air Temperature Increase (FATI) conditions. The patterns of warming included different temperatures (0.5 °C and 0.8 °C), different day-night durations (nighttime, daytime, and the whole day), and different warming stages (WSx) (including WS1 (seedling to tillering), WS2 (jointing to booting), WS3 (heading), WS4 (grain filling to milk ripening)). At harvest, samples of different rice tissues were collected and the Cd concentrations were measured. The results showed that warming significantly increased Cd concentrations in grain by 1.45 and 2.31 times, which was positively correlated with the two temperature increases (0.5 °C and 0.8 °C), respectively. Both daytime and nighttime warming significantly increased the Cd concentration in grain, and the daytime dominated Cd translocation from roots to shoots. In addition, warming in individual growth stages contributed to increases in Cd accumulation in grain by 31.6% (WS1), 15.0% (WS2), 20.6% (WS3), and 32.8% (WS4), respectively. Specifically, warming during the vegetative phase boosted Cd translocation from roots to shoots, while warming during maturation further increased Cd uptake and remobilization into grain. The projected results could provide a new and in-depth understanding of the fate of Cd in soil-rice systems under global warming conditions in Cd contaminated areas.

Acidithiobacillus species mediated mineral weathering promotes lead immobilization in ferric-silica microstructures at sulfidic tailings.

Immobilization and stabilization of heavy metals (HMs) in sulfidic and metallic tailings are critical to long-term pollution control and sustainable ecological rehabilitation. This study aims to unravel immobilization mechanisms of Pb (Ⅱ) in the neoformed hardpan structure resulting from Acidithiobacillus spp. accelerated bioweathering of sulfides in the presence of silicates. It was found that the bioweathered mineral composite exhibited an elevated Pb (Ⅱ) adsorption capacity compared to that of natural weathered mineral composite. A suit of microspectroscopic techniques such as synchrotron-based X-ray Absorption Spectroscopy (XAS), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR) and Field-Emission Scanning Electron Microscope (FE-SEM) indicated that secondary Fe-bearing minerals, functional groups, and surface properties in the neoformed hardpan were key factors contributing to Pb (Ⅱ) adsorption and immobilization in ferric-silica microstructures. The underlying mechanisms might involve surface adsorption-complexation, dissolution-precipitation, electrostatic attraction, and ion exchange. Microbial communities within the muscovite groups undergoing bioweathering processes demonstrated distinctive survival strategies and community composition under the prevailing geochemical conditions. This proof of concept regarding Pb (Ⅱ) immobilization in microbial transformed mineral composite would provide the basis for scaling up trials for developing field-feasible methodology to management HMs pollution in sulfidic and metallic tailings in near future.

Selenium-Mediated Shaping of Citrus Rhizobiome for Promotion in Root Growth and Soil Phosphorus Activation.

Selenium (Se) has been widely reported to affect plant growth, nutrient cycling, and the rhizobiome. However, how Se shapes the rhizobiome and interacts with plants remains largely elusive. Pot and hydroponic experiments were employed to elucidate the regulatory mechanism of Se in the citrus rhizobiome. Compared to the control, soil Se application significantly increased the root biomass (34.7%) and markedly reduced rhizosphere HCl-P, H2O-P, NaHCO3-IP, and residual-P of citrus, which were related to the variation of citrus rhizobiome. Se primarily enriched Proteobacteria and Actinobacteria as well as the phosphorus (P) functional genes phod and pqqc. Further study revealed that Se altered the metabolite profile of root exudate, particularly enhancing the abundance of l-cyclopentylglycine, cycloleucine, l-proline, l-pipecolic acid, and inositol, which played a key role in reshaping the citrus rhizobiome. These metabolites could serve as both nutrient sources and signaling molecules, thus supporting the growth or chemotaxis of the functional microbes. These bacterial taxa have the potential to solubilize P or stimulate plant growth. These findings provide a novel mechanistic understanding of the intriguing interactions between Se, root exudate, and rhizosphere microbiomes, and demonstrate the potential for utilizing Se to regulate rhizobiome function and enhance soil P utilization in citrus cultivation.

Hydroxyl radicals induced mineralization of organic carbon during oxygenation of ferrous mineral-organic matter associations: Adsorption versus coprecipitation.

The iron (Fe) phases have been widely proposed to preserve organic carbon (OC) via adsorption or coprecipitation pathways, however, such role of Fe phases might be largely reversed under redox-fluctuation conditions, especially for Fe(II) minerals-protected OC. In this study, we synthesized the Fe(II)-OC associations via adsorption and coprecipitation using FeCO3 and three types of low-molecular-weight organic compounds (LMWOCs) at different C/Fe molar ratios, and investigated the OC mineralization induced by hydroxyl radicals (OH) during oxygenation processes. Abundant OH can be produced upon oxygenation of FeCO3-LMWOCs associations within 96 h, giving values of 28.49-151.36 µM in adsorption and 12.63-76.41 µM in coprecipitation treatments depended on types of LMWOCs and C/Fe molar ratios. Fe(II) species in coprecipitates with hydroquinone (HQ) mainly transformed into Goethite-like phases after oxygenation, while adsorption samples induced more formation of lower-crystalline Fe phase (e.g., ferrihydrite). The surface-Fe(II) was the primary electron donors to O2, which further induced hydrogen peroxide (H2O2) formation via one- and two-electron transfer pathways. Finally, the produced OH removed 0.55-9.65 and 0.16-85.54 mg L-1 total OC in adsorption and coprecipitation treatments after oxygenation. Collectively, this study highlights that OC associated with Fe(II) minerals might be labile due to the oxidation of formed OH, and the role of Fe phases in OC sequestration may be further re-evaluated under redox fluctuation conditions.

Photooxidation mechanism of As(III) by straw-derived dissolved organic matter.

Straw return-to-field is a common agronomic practice that would affect the physicochemical characteristics of the paddy soil and overlying water, but few studies have focused on the possible impacts of straw return on the conversion of pollutants. In this study, the photooxidation of As(III) in aqueous solution by straw-derived dissolved organic matter (S-DOM) was investigated. The results showed that dissolved organic matter derived from wheat straw (DOMws) and rape straw (DOMrs) exhibited good spectroscopic features and could efficiently oxidize As(III) under irradiation at pH 5.0, with the kobs values of As(III) oxidation being 0.15 h-1 and 0.17 h-1 for DOMws and DOMrs, respectively. Quenching studies indicated that hydroxyl radical (OH) dominated the oxidation of As(III) for both types of dissolved organic matter (DOM), though singlet oxygen (1O2) also played a role in the DOMrs system. Since acidic conditions are favorable for the formation of OH, As(III) oxidation decreased with an increase of pH value. Additionally, the oxidation efficiency of As(III) was inhibited in the presence of NO3- (0.2-2 mM) while enhanced in the presence of Fe(III) (5-50 µM). This study is of great significance for understanding the removal/transformation behavior of pollutants in paddy fields that receive straw return.

Effects of root morphology and leaf transpiration on Cd uptake and translocation in rice under different growth temperature.

With growing concerns on cadmium (Cd) contamination of rice grain from the public, the mechanism about the uptake and translocation of Cd in rice plant has been widely studied in recent years. However, the study about the effects of future warming on rice Cd accumulation was almost neglected. In the paper, hydroponic experiments of Cd exposure in growth chambers under different growth temperature (asymmetric and symmetric warming) were conducted to investigate how warming influenced Cd uptake and translocation in rice seedlings (6 liangyou 9368). The results showed that warming significantly increased Cd accumulation in shoot and root by 62.7 to 122 % and 65.5 to 73.9 %, respectively. Moreover, symmetric warming boosted Cd translocation from root to shoot, while antitranspirant treatment inhibited it significantly. The possible mechanisms may be that warming increased the fine root (diameter ≤ 0.5 mm) surface area and enlarged the active sites on root surface by influencing root morphology growth, thus promoted Cd uptake by root. Meanwhile, warming increased leaf transpiration and boosted the xylem stream from nutrient solution to above organs, thus enhanced Cd translocation. This study may provide new understanding and possible explanations about Cd uptake and translocation in rice plant under future warming.

Effects of warming on uptake and translocation of cadmium (Cd) and copper (Cu) in a contaminated soil-rice system under Free Air Temperature Increase (FATI).

Global warming has received growing attentions about its potential threats to human in recent, however little is known about its effects on transfer of heavy metals in agro-ecosystem, especially for Cd in rice. Pot experiments were conducted to evaluate Cd/Cu translocation in a contaminated soil-rice system under Free Air Temperature Increase (FATI). The results showed that warming gradually decreased soil porewater pH and increased water-soluble Cd/Cu concentration, reduced formation of iron plaque on root surface, and thus significantly increased total uptake of Cd/Cu by rice. Subsequently, warming significantly promoted Cd translocation from root to shoot, and increased Cd distribution percentage in shoot, while Cu was not significantly affected. Enhanced Cd uptake and translocation synergistically resulted in higher rice grain contamination with increasing concentration from 0.27 to 0.65 and 0.14-0.40 mg kg(-1) for Indica and Japonica rice, respectively. However increase of Cu in brown grain was only attributed to its uptake enhancement under warming. Our study provides a new understanding about the food production insecurity of heavy metal contaminated soil under the future global warming.

Effects of different warming patterns on the translocations of cadmium and copper in a soil-rice seedling system.

Heavy-metal-polluted rice poses potential threats to food security and has received great attention in recent years, while how elevated temperature affects the translocation of heavy metals in soil-rice system is unclear. In this study, potting experiments were conducted in plant growth chambers for 24 days to evaluate the effects of different warming patterns on cadmium (Cd) and copper (Cu) migrations in soil-rice seedling system. Rice seedlings were cultivated under four different day/night temperature patterns: 25/18 °C (CK), 25/23 °C (N5), 30/18 °C (D5), and 30/23 °C (DN5), respectively. Non-contaminated soil (CS), Cd/Cu lightly polluted soil (LS), and highly polluted soil (HS) were chosen for experiments. The results showed that different warming patterns decreased soil pH and elevated available soil Cd/Cu concentrations. The shoot and root biomass were increased by 39.0-320 and 28.6-348 %, respectively. Warming induced significant (p < 0.05) increase of Cd/Cu uptake and translocation in rice seedlings, especially for the Cd concentration in shoot. The Cd concentrations of shoot increased by 5-12 times and up to 8 times for LS and HS, respectively. Meanwhile, the Cd concentration of shoot increased with warming while that of root kept unchanged, indicating that warming promoted cadmium translocation from root to shoot (about -four to nine times of CK), while warming changed the Cu concentration of shoot similarly to that of root and had no significant effects on Cu translocations in rice seedlings. Our study may provide improved understanding for Cd/Cu fates in soil-rice system by warming and imply that heavy metals had the higher environmental risk under the future global warming.

Hyperexponential and nonmonotonic retention of polyvinylpyrrolidone-coated silver nanoparticles in an Ultisol.

The increasing application of engineered nanoparticles (ENPs) has heightened the concern that these ENPs would eventually be released to the environment and may enter into life cycle of living beings. In this regard, it is essential to understand how these ENPs transport and retain in natural soils because they are considered to be a major repository for ENPs. Herein, transport and retention of polyvinylpyrrolidone (PVP)-coated silver nanoparticles (PVP-AgNPs) were investigated over a wide range of physicochemical factors in water-saturated columns packed with an Ultisol rich in clay-size particles. Higher mobility of PVP-AgNPs occurred at larger soil grain size, lower solution ionic strength and divalent cation concentration, higher flow rate, and greater PVP concentrations. Most breakthrough curves (BTCs) for PVP-AgNPs exhibited significant amounts of retardation in the soil due to its large surface area and quantity of retention sites. In contrast to colloid filtration theory, the shapes of retention profiles (RPs) for PVP-AgNPs were either hyperexponential or nonmonotonic (a peak in particle retention down-gradient from the column inlet). The BTCs and hyperexponential RPs were successfully described using a 1-species model that considered time- and depth-dependent retention. Conversely, a 2-species model that included reversibility of retained PVP-AgNPs had to be employed to better simulate the BTCs and nonmonotonic RPs. As the retained concentration of species 1 approached the maximum solid-phase concentration, a second mobile species (species 2, i.e., the same PVP-AgNPs that are reversibly retained) was released that could be retained at a different rate than species 1 and thus yielded the nonmonotonic RPs. Some retained PVP-AgNPs were likely to irreversibly deposit in the primary minimum associated with microscopic chemical heterogeneity (favorable sites). Transmission electron microscopy and energy-dispersive X-ray spectroscopy analysis suggested that these favorable sites were positively charged sites on montmorillonite edges and goethite surfaces in the soil. Overall, our study highlights that the transport and especially retention of PVP-AgNPs are highly sensitive to the physicochemical factors, but mathematical modeling can accurately predict the fate of these ENPs in porous media which is important for better understanding the fate of these ENPs in point of exit and in the environment.

[Carbon storage of forest stands in Shandong Province estimated by forestry inventory data].

Based on the 7th forestry inventory data of Shandong Province, this paper estimated the carbon storage and carbon density of forest stands, and analyzed their distribution characteristics according to dominant tree species, age groups and forest category using the volume-derived biomass method and average-biomass method. In 2007, the total carbon storage of the forest stands was 25. 27 Tg, of which the coniferous forests, mixed conifer broad-leaved forests, and broad-leaved forests accounted for 8.6%, 2.0% and 89.4%, respectively. The carbon storage of forest age groups followed the sequence of young forests > middle-aged forests > mature forests > near-mature forests > over-mature forests. The carbon storage of young forests and middle-aged forests accounted for 69.3% of the total carbon storage. Timber forest, non-timber product forest and protection forests accounted for 37.1%, 36.3% and 24.8% of the total carbon storage, respectively. The average carbon density of forest stands in Shandong Province was 10.59 t x hm(-2), which was lower than the national average level. This phenomenon was attributed to the imperfect structure of forest types and age groups, i. e., the notably higher percentage of timber forests and non-timber product forest and the excessively higher percentage of young forests and middle-aged forest than mature forests.

Electrokinetic delivery of persulfate to remediate PCBs polluted soils: effect of injection spot.

Persulfate-based in situ chemical oxidation (ISCO) is a promising technique for the remediation of organic compounds contaminated soils. Electrokinetics (EK) provides an alternative method to deliver oxidants into the target zones especially in low permeable-soil. In this study, the flexibility of delivering persulfate by EK to remediate polychlorinated biphenyls (PCBs) polluted soil was investigated. 20% (w/w) of persulfate was injected at the anode, cathode and both electrodes to examine its transport behaviors under electrical field, and the effect of field inversion process was also evaluated. The results showed that high dosage of persulfate could be delivered into S4 section (near cathode) by electroosmosis when persulfate was injected from anode, 30.8% of PCBs was removed from the soil, and the formed hydroxyl precipitation near the cathode during EK process impeded the transportation of persulfate. In contrast, only 18.9% of PCBs was removed with the injection of persulfate from cathode, although the breakthrough of persulfate into the anode reservoir was observed. These results indicated that the electroosmotic flow is more effective for the transportation of persulfate into soil. The addition of persulfate from both electrodes did not significantly facilitate the PCBs oxidation as well as the treatment of electrical field reversion, the reinforced negative depolarization function occurring in the cathode at high current consumed most of the oxidant. Furthermore, it was found that strong acid condition near the anode favored the oxidation of PCBs by persulfate and the degradation of PCBs was in consistent with the oxidation of Soil TOC in EK/persulfate system.