A chrysotile-based Fe/Ti nanoreactor enables efficient arsenic capture for sustainable environmental remediation.

Iron-based materials for arsenic (As) immobilization in practical groundwater and soil remediation suffer from a low removal capacity and an insufficient long-term stability. Herein, a unique chrysotile-based nanoreactor has been developed by incorporating iron/titanium oxides into the cylindrical cavity of chrysotile (TiFe-Chy), providing sufficient internal reaction sites for As immobilization. Results reveal that the adsorption capacities of TiFe-Chy for As(III) and As(V) are considerably higher than the commonly used amendments, i.e., layered double hydroxide (LDH) and Phoslock®, respectively. More importantly, TiFe-Chy exhibits a strong anti-interference capability of As immobilization in soils compared to those commercial products due to this unique incorporation approach. Fixed-bed leaching experiments indciate that this TiFe-Chy nanoreactor can efficiently decrase the As(III) and As(V) concentrations by 81.8-87.3% within a period of ten years, significantly improving the long-term stability of As immobilization in soils. Life cycle assessment analysis reveals that TiFe-Chy can reduce negative environmental impacts (such as carbon emissions), resulting in a low cost for soils and groundwater remediation. The findings of this work open a new avenue for sustainable heavy metal(loid)s remediation in groundwater and soils.

The nature of metal atoms incorporated in hematite determines oxygen activation by surface-bound Fe(II) for As(III) oxidation.

The incorporation of secondary metal atoms into iron oxyhydroxides may regulate the surface chemistry of mediating electron transfer (ET) and, therefore, the biogeochemical pollutant processes such as arsenic (As) in the subsurface and soils. The influence of incorporating two typical metals (Cu and Zn) into a specific {001} hematite facet on O2 activation by surface-bound Fe(II) was addressed. The results showed that Cu-incorporated hematite enhances As(III) oxidation in the presence of Fe(II) under oxic conditions and increases with increasing Cu content. Conversely, Zn incorporation leads to the opposite trend. The As(III) oxidation induced by surface-bound Fe(II) is positively related to the Fe(II) content and is favorable under acidic conditions. Reactive oxygen species (ROS), such as superoxide (·O2-) and H2O2, predominantly contribute to As(III) oxidation as a result of 1-electron transfer from bound Fe(II) to surface O2 on hematite and radical propagation. Electrochemical analysis demonstrates that Cu incorporation significantly lower the oxidation potential of Fe(II) on hematite, whereas Zn led to a higher reaction potential for Fe(II) oxidation. Subsequently, distinct surface reactivities of hematite for the activation of O2 to form ROS by surface-bound Fe(II) are evidenced by metal incorporation. Our study provides a new understanding of the changes in the surface chemistry of iron oxyhydroxides because of incorporating metals (Zn and Cu), and therefore impact the biogeochemical processes of pollutants in soils and subsurface environments.

Phase transformation of nanosized zero-valent iron modulated by As(III) determines heavy metal passivation.

Nanoscale zero-valent iron (nZVI) has been extensively used for the passivation of cadmium (Cd) or arsenic (As) from wastewaters, while the underlying mechanisms of nZVI reaction with coexisting Cd and As are largely overlooked. Herein, the interactions of Cd and As during the course of nZVI transformation and the corresponding effects on respective pollutant removal have been systematically investigated. Batch experiments results show that As(III) addition significantly promotes the passivation of Cd(II) by nZVI, and the removal capacity increases by 7.8 times compared to that of Cd(II) alone. However, the adsorption and oxidative transformation of As(III) are barely affected under a relatively low Cd(II) concentration. It is conducive to the adsorption of Cd(II) and As(III) using nZVI under neutral conditions. The transformation of nZVI to lepidocrocite dominates in the Cd(II) single system, while it mainly converts to amorphous Fe oxyhydroxide with the addition of As(III). As(III) notably reduces the surface charge of Fe oxyhydroxide intermediates and to form the ternary complexes with Cd (Fe-As-Cd), which is the predominant mechanism for the promoted Cd(II) passivation. This work provides new understanding of nZVI transformation coupled to Cd(II) and As(III) passivation, which are likely contributing to the heavy metalloids regulation in waters and subsurface environments.

Biogeochemical Fe(II) generators as a new strategy for limiting Cd uptake by rice and its implication for agricultural sustainability.

This work has developed a new strategy of biogeochemical Fe(II) generators for activating microbial Fe(II) generation to immobilize Cd in soils through protons scavenging and coprecipitation. A new biochar modified magnetite (FeBC15) has been fabricated through a top-down method, with which microbial respiration can be stimulated in paddy soil. The FeBC15 exhibits a higher adsorption capacity for Cd than pristine magnetite (1.7 times). The results show that the available Cd can be reduced by 14.4% after adding FeBC15 compared to the control. More importantly, FeBC15 particles promote the conversion of MgCl2 - Cd to stable crystalline Fe/Al bound Cd under the incubation period. The enhanced pH and Fe(II) leads to a comparably lower Cd availability in soils than in pristine soils, which are supported by the enhanced relative abundance of Geobacter and Clostridium with the FeBC15 treatment (i.e. up to 7.44-7.68 × 109 copies/g soil). The Diffusive Gradients in Thin-films (DGT) study indicates that FeBC15 can lower the replenish capacity of soils (i.e. KdL values of 0.2-3.6 mL/g) to soil pore waters and limit root absorption. Pot experiments demonstrate that this strategy can alleviate the rice Cd content by 38.4% (< 0.2 mg/kg). This work paves a new pathway for reducing Cd uptake in rice, enabling sustainable remediation of paddy soil.

A meta-analysis of heavy metal bioavailability response to biochar aging: Importance of soil and biochar properties.

Biochar has been widely applied to remediate the heavy metal-polluted soils, whereas biochar aging can induce the changes of the biochar physic-chemical properties. Afterwards, the bioavailability of heavy metals (BHM) will vary in soils which likely increase the unstable fractions of heavy metals and the following environmental risks. To explore the biochar aging effects on the BHM changes in responses to the variation of experimental conditions and biochar properties, a meta-analysis for the literatures published before May 2020 was conducted. A sum of 257 independent observations from 22 published papers was obtained. The results from the analysis of boosted regression tree showed that the soil pH was the most important factor influencing the BHM changes in biochar amended soil, followed by soil texture, aging time and biochar pyrolysis temperature. The results of this review showed that the BHM was decreased by 16.9%, 28.7% and 6.4% in weakly acid soil (pH 6.00-6.99), coarse- and medium-textured soils, respectively, but increased by 149% and 121% in the alkaline (pH > 8.00) and fine-textured soils. The BHM declined in the soils amended with biochar pyrolyzed at relative high temperature (> 500 °C), and increased during aging in soils amended with biochar pyrolyzed at relatively low temperature (401-500 °C). In terms of diverse immobilized heavy metals, only bioavailable Zn in soil decreased after aging. However, there was no significant changes in Cd, Cu and Pb's bioavalability. Besides, the BHM was decreased by 18.6% within the short-term (less than one year) biochar aging, while showed inverse trend during the longer aging processes. Besides, the application of lignin-enriched biochar may counteract the positive effects of the biochar aging on BHM. Our works may promote the interpretation of the interference factors on the BHM changes and filled the research gaps on biochar aging process in soils.

[Clinicopathologic features and proliferative status of colorectal serrated lesions: a study of 104 cases].

OBJECTIVE: To study the clinicopathologic features and proliferative status of colorectal hyperplastic polyp (HP), sessile serrated adenoma (SSA) and traditional serrated adenoma (TSA). METHODS: One hundred and four cases colorectal serrated lesions were collected from 2628 cases of colorectal polyps during the period from November, 2002 to December, 2007. The clinicopathologic features and expression of proliferation marker Ki-67 were studied. RESULTS: On the basis of morphologic examination, 60 cases were classified as HP, 20 cases as TSA, 11 cases as SSA, 7 cases as mixed HP/SSA/TSA, and 6 cases as mixed serrated polyp/adenoma and tubular adenoma. Immunohistochemical study for Ki-67 showed that 40 cases (78%) of the 51 cases of HP were either mostly negative or rarely (<25% cells) positive. Most of the positive cells were located at crypt bases. Among the 15 cases of TSA, 11 of them revealed positive cryptal cells (25% to 50% or>50% positivity). Most of the positive cells were located in mid portion of crypts. The number and distribution of Ki-67 positive cells in SSA were similar to those in TSA but were significantly different from those in tubular adenoma and adenocarcinoma (chi2=34.601, P=0.000; chi2=63.077, P=0.000, respectively). CONCLUSIONS: HP, SSA and TSA have their morphologic characteristics, with some overlapping features noted. The distinction between SSA and HP can be difficult. Diagnosis of SSA relies mostly on architectural rather than cytologic features. The distinction between TSA and SSA depends mainly on the presence of dysplasia. Ectopic crypt formation is almost exclusively seen in TSA. The distribution and percentage of Ki-67-positive cells are also helpful in subtyping of various colorectal serrated lesions. In general, the proliferative index is lower in serrated adenoma (TSA or SSA) than in tubular adenoma.

[Clinicopathological and immunohistochemical features of colorectal sessile serrated adenoma].

OBJECTIVE: To investigate the clinicopathological characteristics and expression status of Ki67, p53, CEA, CDX, CK7 in colorectal sessile serrated adenoma (SSA). METHODS: The clinicopathological data of 11 cases of SSA, 51 cases of hyperplastic polyp (HP) and one case with mixed HP/SSA were reviewed and analyzed retrospectively. The expression of Ki67, p53, CEA, CDX and CK7 were detected by immunohistochemistry. RESULTS: The major histological features in SSA were architectural abnormality in crypts, dilatation of serrated crypt bases like an inverted "T" or "L" shape adjacent to muscularis mucosa. Atypical cells containing round to oval nuclei and nucleoli were also observed. The immunohistochemical staining showed that the expression of p53 increased gradually from HP to TA: 11.8% in HP, 20.0% in SSA, 41.2% in VTA and 75.0% in TA, with a significant difference among the groups (chi(2) = 17.996, P = 0.000). However, no significant difference in the expression of CDX and CK7 was observed between HP and SSA. Of the 10 SSA cases, positive expression of Ki67 was found in cells located in the base or middle part of crypt in 6 cases, positive cells index was 26% - 50% in 5 cases, and > 50% in 3. Compared with the expression of Ki67 in the HP, VTA and VA, SSA showed a significant difference in both the positive cell number and in the positive regions. (positive number: chi(2) = 34.601, P = 0.000; positive regions: chi(2) = 63.077, P = 0.000). CONCLUSION: Morphological diagnosis of SSA was mainly based on crypt architectural and cellular abnormalities, and the crypt architectural abnormality may be more important than cellular features. Detection of p53 and Ki67 expression may be helpful in differential diagnosis and understanding the nature of SSA.

Blood pressure change with age in salt-sensitive teenagers.

OBJECTIVE: To observe blood pressure change with age in salt-sensitive teenagers whose salt sensitivity were determined by repeated testing. METHODS: Salt sensitivity was determined through intravenous infusion of normal saline combined with volume-depletion by oral diuretic furosemide in 55 teenagers. After five years, salt sensitivity was re-examined and subject blood pressure was followed up. Blood pressure changes in salt-sensitive teenagers were compared to that of non-salt sensitive teenagers over five years. RESULTS: After 5 years, the repetition rate of salt sensitivity determined by intravenous saline loading is 92.7%. In teenagers with salt sensitivity on the baseline, both the systolic blood pressure increments and increment rates were much higher than non-salt sensitive teenagers (12.7 +/- 12.1 mmHg vs. 2.8 +/- 5.2 mmHg, P < 0.01; 12.2% +/- 12.0% vs. 2.5% +/- 4.4%, P < 0.001, respectively). There was a similar trend for diastolic blood pressure (8.4 +/- 6.4 mmHg vs. 3.7 +/- 6.4 mmHg, P = 0.052; 13.2% +/- 10.6% vs. 6.8% +/- 10.1%, P = 0.053, respectively). CONCLUSIONS: Salt sensitivity determined by intravenous saline loading showed good reproducibility. Blood pressure increments with age were much higher in salt-sensitive teenagers than non-salt sensitive teenagers, especially in terms of systolic blood pressure.

[Long term observation in effects of potassium and calcium supplementation on arterial blood pressure and sodium metabolism in adolescents with higher blood pressure].

OBJECTIVE: To investigate the effects of potassium and calcium supplementation in table salt on reduction of arterial blood pressure and sodium metabolism in adolescents with higher blood pressure. METHODS: A single blind placebo-controlled trial was carried out for two years in 220 adolescents with higher blood pressure, aged 18 - 22 years, who were randomly divided into supplementary group (n = 110) and control group (n = 110). Each of the subjects in the supplementary group and their family members was given 10 mmol of potassium and 10 mmol of calcium mixed in their table salt daily for 24 months. RESULTS: Night urinary sodium and potassium excretion increased (urinary Na(+), P < 0.05; urinary K(+), P < 0.01) and blood pressure lowered by 5.3 mm Hg/1.8 mm Hg in average from the baseline in the supplementary group two years after potassium and calcium supplementation, as compared with that in the control group increased by (1.3/1.7) mm Hg. CONCLUSIONS: Adequate supplement of potassium and calcium in daily table salt intake was an effective way to prevent form hypertension and could promote their urinary sodium excretion and reduction of arterial blood pressure in adolescents with higher blood pressure.