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Cross-linked sulfydryl-functionalized graphene oxide as ultra-high capacity adsorbent for high selectivity and ppb level removal of mercury from water under wide pH range
2021
Bao, Shuangyou | Wang, Yingjun | Yu, Yongsheng | Yang, Weiwei | Sun, Yinyong
It is highly desirable but remains extremely challenging to develop a facile strategy to prepare adsorbent for dealing with heavy metal pollution in water. Here, we report a facile approach for preparing sulfydryl-functionalized graphene oxide (S-GO) by cross-linking method with an unprecedented adsorption capacity and ultrahigh selectivity for efficient Hg(II) removal. The adsorbents exhibit a prominent performance in capturing Hg(II) from wastewater with a record-high adsorption capacity of 3490 mg/g and rapid kinetics to reduce Hg(II) contaminants below the discharge standard of drinking water (2 ppb) within 60 min under a wide pH range even in the coexistent of other interfering metal ions. In addition, the adsorbents can be also easily recycled and reused multiple times with no apparent decline in removal efficiency. Considering the broad diversity, we developed also a magnetic Fe₃O₄/S-GO adsorbent by a simple chemical cross-linking reaction to achieve rapid separation of S-GO from their aqueous solution. In addition, the adsorbents were successfully applied in dealing with the practical industrial wastewater. The results indicate the potential of rationally designed sulfydryl-functionalized graphene oxide for high performance Hg(II) removal.
Show more [+] Less [-]Ammonium-nitrogen addition at the seedling stage does not reduce grain cadmium concentration in two common wheat (Triticum aestivum L.) cultivars
2021
Cheng, Yiran | Yang, Tian | Xiang, Wenhui | Li, Siyu | Fan, Xing | Sha, Lina | Kang, Houyang | Wu, Dandan | Zhang, Haiqin | Zeng, Jian | Zhou, Yonghong | Wang, Yi
High cadmium (Cd) concentration in common wheat (Triticum aestivum L.) grains poses potential health risks. Several management strategies have been used to reduce grain Cd concentration. However, limited information is available on the use of ammonium-nitrogen (NH₄⁺-N) as a strategy to manage Cd concentration in wheat grains. In this study, NH₄⁺-N addition at the seedling stage unchanged the grain Cd concentration in the high-Cd accumulator, Zhoumai 18 (ZM18), but dramatically increased that in the low-Cd accumulator, Yunmai 51 (YM51). Further analysis revealed that the effects of NH₄⁺-N addition on whole-plant Cd absorption, root-to-shoot Cd translocation, and shoot-to-grain Cd remobilization were different between the two wheat cultivars. In ZM18, NH₄⁺-N addition did not change whole-plant Cd absorption, but inhibited root-to-shoot Cd translocation and Cd remobilization from lower internodes, lower leaves, node 1, and internode 1 to grains via the down-regulation of yellow stripe-like transporters (YSL), zinc transporters (ZIP5, ZIP7, and ZIP10), and heavy-metal transporting ATPases (HMA2). This inhibition decreased the grain Cd content by 29.62%, which was consistent with the decrease of the grain dry weight by 23.26%, leading to unchanged grain Cd concentration in ZM18. However, in YM51, NH₄⁺-N addition promoted continuous Cd absorption during grain filling, root-to-shoot Cd translocation and whole-plant Cd absorption. The absorbed Cd was directly transported to internode 1 via the xylem and then re-transported to grains via the phloem by up-regulated YSL, ZIP5, and copper transporters (COPT4). This promotion increased the grain Cd content by 245.35%, which was higher than the increased grain dry weight by 132.89%, leading to increased grain Cd concentration in YM51. Our findings concluded that the addition of NH₄⁺-N fertilizer at the seedling stage is not suitable for reducing grain Cd concentration in common wheat cultivars.
Show more [+] Less [-]Foliar application of the sulfhydryl compound 2,3-dimercaptosuccinic acid inhibits cadmium, lead, and arsenic accumulation in rice grains by promoting heavy metal immobilization in flag leaves
2021
Yang, Xiaorong | Wang, Changrong | Huang, Yongchun | Liu, Bin | Liu, Zhongqi | Huang, Yizong | Cheng, Liulong | Huang, Yanfei | Zhang, Changbo
Mixed pollution due to heavy metals (HMs), especially cadmium (Cd), lead (Pb), and arsenic (As), seriously endangers the safety of food produced in paddy soil. In the field experiments, foliar application of 2,3-dimercaptosuccinic acid (DMSA) at the flowering stage was found to significantly reduce the levels of Cd, Pb, total As, and inorganic As (iAs) in rice grains by 47.95%, 61.76%, 36.37%, and 51.24%, respectively, without affecting the concentration of metallonutrients, including Mn, K, Mg, Ca, Fe, and Zn. DMSA treatment significantly reduced the concentrations of Cd, Pb, and As in the panicle node, panicle neck, and rachis, while those in the flag leaves were significantly increased by up to 20.87%, 49.40%, and 32.67%, respectively. DMSA application promoted the transport of HM from roots and lower stalks to flag leaves with a maximum increase of 34.55%, 52.65%, and 46.94%, respectively, whereas inhibited the transport of HM from flag leaves to panicle, rachis, and grains. Therefore, foliar application of DMSA reduced Cd, Pb, and As accumulation in rice grains by immobilizing HMs in flag leaves. Thus, this strategy could act as a promising agronomic measure for the remediation of mixed HM contamination in paddy fields.
Show more [+] Less [-]Passerine bird reproduction does not decline in a highly-contaminated mercury mining district of China
2021
Su, Tongping | He, Chao | Jiang, Aiwu | Xu, Zhidong | Goodale, Eben | Qiu, Guangle
Mercury (Hg) is a neurotoxic element with severe effects on humans and wildlife. Widely distributed by atmospheric deposition, it can also be localized near point sources such as mines. Mercury has been shown to reduce the reproduction of bird populations in field observations in North America and Europe, but studies are needed in Asia, where the majority of emissions now occur. We investigated the reproduction of two passerines, Japanese Tit (Parus minor) and Russet Sparrow (Passer rutilans), in a large-scale Hg mining district, and a non-mining district, both in Guizhou, southwest China. Concentrations of Hg were elevated in the mining district (blood levels of 2.54 ± 2.21 [SD] and 0.71 ± 0.40 μg/g, in adult tits and sparrows, respectively). However, we saw no evidence of decreased breeding there: metrics such as egg volume, nestling weight, hatching and fledgling success, were all similar between the different districts across two breeding seasons. Nor were there correlations at the mining district between Hg levels of adults or juveniles, and hatching or fledgling success, or nestling weight. Nest success was high even in the mining district (tit, 64.0%; sparrow: 83.1%). This lack of reproductive decline may be related to lower blood levels in nestlings (means < 0.15 μg/g for both species). Concentrations of selenium (Se), and Se-to-Hg molar ratio, were also not correlated to breeding success. Although blood levels of 3.0 μg/g have been considered as a threshold of adverse effects in birds, even leading to severe effects, we detected no population-level reproductive effects, despite ~25% of the adult tits being above this level. Future work should investigate different locations in the mining district, different life-stages of the birds, and a wider variety of species. The hypothesis that bird populations can evolve resistance to Hg in contaminated areas should also be examined further.
Show more [+] Less [-]Effect of heavy metal-induced stress on two extremophilic microbial communities from Caviahue-Copahue, Argentina
2021
Massello, Francisco L. | Donati, Edgardo
Metal pollution is a great concern worldwide and the development of new technologies for more sustainable extraction methods as well as for the remediation of polluted sites is essential. Extremophilic microorganisms are attractive for this purpose since they have poly-resistance mechanisms which make them versatile. In this work, we sampled an acidic river and a hot spring of Caviahue-Copahue volcanic environment. The indigenous microbial communities were exposed to five heavy metals (Cd, Co, Cu, Ni and Zn) in batch-cultures favouring different metabolisms of biotechnological interest. Remarkably, high tolerance values were reached in all the cultures, even though most of the metals studied were not present in the environmental sample. Particularly, outstanding tolerances were exhibited by acidophiles, which grew at concentrations as high as 400 mM of Zn and Ni. High-throughput amplicon sequencing of 16S rRNA gene was used to study the indigenous communities and the resistant consortia. We took three approaches for the analysis: phylotypes, OTUs and amplicon sequence variants (ASVs). Interestingly, similar conclusions were drawn in all three cases. Analysing the phylogenetic structure and functional potential of the adapted consortia, we found that the strongest selection was exerted by the culture media. Notably, there was a poor correlation between alpha diversity and metal stress; furthermore, metal stress did not seem to harm the functional potential of the consortia. All these results reveal a great adaptability and versatility. At the end, 25 metal-resistant extremophilic consortia with potential uses in bioremediation, bioleaching or biomonitoring processes were obtained.
Show more [+] Less [-]Microlophus atacamensis as a biomonitor of coastal contamination in the Atacama Desert, Chile: An evaluation through a non-lethal technique
2021
In this report, we investigated the accumulation of heavy metals in the lizard Microlophus atacamensis, in three coastal areas of the Atacama Desert, northern Chile. We captured reptiles in a non-intervened area (Parque Nacional Pan de Azúcar, PAZ), an area of mining impact (Caleta Palitos, PAL) and an active industrial zone (Puerto de Caldera, CAL). Our methods included a non-lethal sampling of reptiles’ tails obtained by autotomy and a few sacrificed animals to perform a stomach contents analysis. The concentrations of lead, copper, nickel, zinc and cadmium were measured by atomic absorption spectrophotometry in both soil and prey and compared to those recorded in the lizards’ tails. Data obtained from lizard tails captured in PAL showed significantly high concentrations of Pb, Cu, Ni, and Zn compared to the other two sites PAZ and CAL. We did not find statistically significant differences among PAZ, PAL and CAL soils, probably due to the similar geological composition of the sites. However, the regional background values for Pb indicate contamination or at least metal enrichment in soils of the three sites, for Cu the global background values indicate contamination for the three sites, and for Cd both the regional and global backgroud values show high values. The analysis of the stomach content showed differences in the food sources of the lizards among the sites studied. The concentration of heavy metal in lizard tissues versus prey delivered values of the Trophic Transfer Factor higher than one (1), suggesting that food may be a primary source of metals in the tissues of M. atacamensis. Calculations of the Bioaccumulation Factor (BAF) and the Ecological Risk (IR) resulted in values higher than one (1) indicating the relevance of this process in the sites studied. In this article, we report relationships between environmental contaminants, mainly putative preys, and concentrations found in lizard tails, which is more substantial in areas with historical heavy metal contamination such as PAL where the non-lethal technique developed in this research suggests a process of metal bioaccumulation in M. atacamensis.
Show more [+] Less [-]Identification of a rice metallochaperone for cadmium tolerance by an epigenetic mechanism and potential use for clean up in wetland
2021
Feng, Sheng Jun | Liu, Xue Song | Cao, Hong Wei | Yang, Zhi Min
Cadmium (Cd) is a toxic heavy metal that initiates diverse chronic diseases through food chains. Developing a biotechnology for manipulating Cd uptake in plants is beneficial to reduce environmental and health risks. Here, we identified a novel epigenetic mechanism underlying Cd accumulation regulated by an uncharacterized metallochaperone namely Heavy Metal Responsive Protein (HMP) in rice plants. OsHMP resides in cytoplasm and nucleus, dominantly induced by Cd stress and binds directly to Cd ions. OsHMP overexpression enhanced the rice growth under Cd stress but accumulated more Cd, whereas knockout or knockdown of OsHMP showed a contrasting effect. The enhanced Cd accumulation in the transgenic lines was confirmed by a long-term experiment with rice growing at the environmentally realistic Cd concentration in soil. The bisulfite sequencing and chromatin immunoprecipitation assessments revealed that Cd stress reduced significantly the DNA methylation at CpG (Cytosine-Guanine) and histone H3K9me2 marks in the upstream of OsHMP. By identifying a couple of mutants defective in DNA methylation and histone modification (H3K9me2) such as Osmet1 (methylatransfease1) and Ossdg714 (kryptonite), we found that the Cd-induced epigenetic hypomethylation at the region was associated with OsHMP overexpression, which consequently led to Cd detoxification in rice. The causal relationship was confirmed by the GUS reporter gene coupled with OsHMP and OsMET1 whereby OsMET1 repressed directly the OsHMP expression. Our work signifies that expression of OsHMP is required for Cd detoxification in rice plants, and the Cd-induced hypomethylation in the specific region is responsible for the enhanced OsHMP expression. In summary, this study gained an insight into the epigenetic mechanism for additional OsHMP expression which consequently ensures rice adaptation to the Cd-contaminated environment.
Show more [+] Less [-]Evaluation of stabilizing material and stabilization efficiency through comparative study of toxic heavy metal transfer between corn and peanut grown in stabilized field soil
2021
Lee, Yonghyeon | Cui, Mingcan | Son, Younggyu | Ma, Junjun | Han, Zhengchang | Khim, Jeehyeong
Soil contaminated with toxic heavy metals (THMs) was stabilized by adding a combination of waste resources in 7.0 wt%, including coal-mine drainage sludge, waste cow bone, and steelmaking slag, in the ratio of 5:35:60. Subsequently, corn and peanut were cultivated in treated soil to investigate the effects of the waste resources on THM mobility in soil and translocation to plants. Sequential extraction procedures (SEP) was used to analyze mobile phase THMs which could be accumulated in the plants. SEP shows that mobile Pb, Cd, Cu, Zn, Ni, Cr, and As were reduced by 8.48%, 29.22%, 18.85%, 21.66%, 4.58%, 62.78%, and 20.01%, respectively. The bioaccumulation of THMs was clearly hindered by stabilization; however, the increment in the amount of immobile-phase THMs and change in the amount of translocated THMs was not proportional. The corn grains grown above the soil surface were compared with the peanut grains grown beneath the soil surface, and the results indicating that the efficiency of stabilization on THM translocation may not depend on the contact of grain to soil but the nature of plant. Interestingly, the results of bioaccumulation with and without stabilization showed that the movement of some THMs inside the plants was affected by stabilization.
Show more [+] Less [-]Ecological and health risk assessments and water quality criteria of heavy metals in the Haihe River
2021
Cui, Liang | Wang, Xiaonan | Li, Ji | Gao, Xiangyun | Zhang, Jiawen | Liu, Zhengtao
Heavy metal pollution is an issue of wide concern owing to the toxic and bioaccumulative properties of many heavy metals and their tendencies to persist in the environment. The Haihe River is an important river in the Beijing–Tianjin–Hebei region, and heavy metal pollution of the basin has attracted considerable attention. This study determined the concentrations of 14 heavy metals (As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, and Zn) in water, sediments, and fish samples from the Haihe River basin. The results showed that the concentrations ranged from 0.08 μg L⁻¹ to 60.49 μg L⁻¹ in water, 0.11 mg kg⁻¹ to 229.20 mg kg⁻¹ in sediments, and 0.01 mg kg⁻¹ to 11.72 mg kg⁻¹ in fish. We derived the ambient water quality criteria (AWQC) value of each heavy metal with respect to human health, and then performed a comprehensive risk assessment according to the native parameters. The human health AWQC values for the assessed 14 heavy metals ranged from 0.16 μg L⁻¹ to 726.53 μg L⁻¹. The health risks posed by As, Cr, Hg, and Sb and the ecological risks associated with Ni, Cu, Cr, Zn, Cd, Co, Hg, and Sn were found to be issues of concern. The results of a sensitivity analysis revealed that the highest contributing parameter was i) the concentration in water (Cw) for Cd, Co, Mn, Sb, and Sn; ii) the intake rate of water (IRw) for As, Ba, Cr, Hg, Ni, Pb, and Se; and iii) the concentration in fish (Cf) for Cu and Zn. The results of this research could contribute to the information required for water quality assessments and the development of water quality standards.
Show more [+] Less [-]Reveal the metal handling and resistance of earthworm Metaphire californica with different exposure history through toxicokinetic modeling
2021
Huang, Caide | Ge, Yan | Shen, Zhiqiang | Wang, Kun | Yue, Shizhong | Qiao, Yuhui
Toxicokinetic (TK) model provides a new approach to mechanistically elucidate the natural variation of metal handling strategy by adaptive and sensitive earthworm populations. Here, TK model was applied to explore the metal handling and resistance strategy of wild Metaphire californica with different historical exposure history through a 12-day re-exposure and another 12-day elimination incubation. M. californica populations showed different kinetic strategies for non-essential metals (Cd and Pb) and essential metals (Zn and Cu), which were closely related to their exposure history. M. californica from the most serious Cd-contaminated soil showed the fastest kinetic rates of both Cd uptake (K₁ = 0.78 gₛₒᵢₗ/gwₒᵣₘ/day) and elimination (K₂ = 0.23 day⁻¹), and also had the lowest Cd half-life (t₁/₂ = 3.01 day), which demonstrated the potential Cd-resistance of wild M. californica from Cd-contaminated soils. Besides, the comparative experiment showed totally different metal kinetics of laboratory Eisenia fetida from field M. californica, suggesting the impacts of distinct exposure history and species-specifical sensitivities. These findings provide a novel approach to identify and quantify resistance using TK model and also imply the risk of overlooking existing exposure background and interspecies extrapolation in eco-toxicological studies and risk assessments.
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