Synthesis and potential applications of cyclodextrin-based metal–organic frameworks: a review

Metal–organic frameworks are porous polymeric materials formed by linking metal ions with organic bridging ligands. Metal–organic frameworks are used as sensors, catalysts for organic transformations, biomass conversion, photovoltaics, electrochemical applications, gas storage and separation, and photocatalysis. Nonetheless, many actual metal–organic frameworks present limitations such as toxicity of preparation reagents and components, which make frameworks unusable for food and pharmaceutical applications. Here, we review the structure, synthesis and properties of cyclodextrin-based metal–organic frameworks that could be used in bioapplications. Synthetic methods include vapor diffusion, microwave-assisted, hydro/solvothermal, and ultrasound techniques. The vapor diffusion method can produce cyclodextrin-based metal–organic framework crystals with particle sizes ranging from 200 nm to 400 μm. Applications comprise food packaging, drug delivery, sensors, adsorbents, gas separation, and membranes. Cyclodextrin-based metal–organic frameworks showed loading efficacy of the bioactive compounds ranging from 3.29 to 97.80%.

     

Activated carbons and amine-modified materials for carbon dioxide capture — a review

Rapidly increasing concentration of CO₂ in the atmosphere has drawn more and more attention in recent years, and adsorption has been considered as an effective technology for CO₂ capture from the anthropogenic sources. In this paper, the attractive adsorbents including activated carbons and amine-modified materials were mainly reviewed and discussed with particular attention on progress in the adsorbent preparation and CO₂ adsorption capacity. Carbon materials can be prepared from different precursors including fossil fuels, biomass and resins using the carbonization-activation or only activation process, and activated carbons prepared by KOH activation with high CO₂ adsorbed amount were reviewed in the preparation, adsorption capacity as well as the relationship between the pore characteristics and CO₂ adsorption. For the amine-modified materials, the physical impregnation and chemical graft of polyethylenimine (PEI) on the different porous materials were introduced in terms of preparation method and adsorption performance as well as their advantages and disadvantages for CO₂ adsorption. In the last section, the issues and prospect of solid adsorbents for CO₂ adsorption were summarized, and it is expected that this review will be helpful for the fundamental studies and industrial applications of activated carbons and amine-modified adsorbents for CO₂ capture.     

Nanoconfinement engineering for enchanced adsorption of carbon materials,metal–organic frameworks,mesoporous silica,MXenes and porous organic polymers: a review

In material synthesis, nanoconfinement acts both as a physical reactor to tune the shape and size of nanomaterials, and as a chemical microenvironment for the nucleation and growth of nanoconfined substances, resulting in unique material properties. This nanoconfinement effect has been extensively applied to synthesize materials for hydrogen storage, catalysis and separation for environmental protection. Here, we review methods to construct nanoconfined space in carbon materials, metal–organic frameworks, mesoporous silica, porous organic polymers and MXenes, a class of two-dimensional inorganic compounds. We discuss nanoconfinement for enhanced adsorption with focus on covering size and dispersion, crystallization and stability, confined water and coordination.

     

Water budget and the consequent duration of canopy carbon gain in a teak plantation in a dry tropical region: Analysis using a soil–plant–air continuum multilayer model

A soil–plant–air continuum multilayer model was used to numerically simulate canopy net assimilation (A_n), evapotranspiration (ET), and soil moisture in a deciduous teak plantation in a dry tropical climate of northern Thailand to examine the influence of soil drought on A_n. The timings of leaf flush and the end of the canopy duration period (CDP) were also investigated from the perspective of the temporal positive carbon gain. Two numerical experiments with different seasonal patterns of leaf area index (LAI) were carried out using above-canopy hydrometeorological data as input data. The first experiment involved seasonally varying LAI estimated based on time-series of radiative transmittance through the canopy, and the second experiment applied an annually constant LAI. The first simulation captured the measured seasonal changes in soil surface moisture; the simulated transpiration agreed with seasonal changes in heat pulse velocity, corresponding to the water use of individual trees, and the simulated A_n became slightly negative. However, in the second simulation, A_n became negative in the dry season because the decline in stomatal conductance due to severe soil drought limited the assimilation, and the simultaneous increase in leaf temperature increased dark respiration. Thus, these experiments revealed that the leaflessness in the dry season is reasonable for carbon gain and emphasized the unfavorable soil water status for carbon gain in the dry season. Examining the duration of positive A_n (DPA) in the second simulation showed that the start of the longest DPA (LDPA) in a year approached the timing of leaf flush in the teak plantation after the spring equinox. On the other hand, the end appeared earlier than that of all CDPs. This result is consistent with the sap flow stopping earlier than the complete leaf fall, implying that the carbon assimilation period ends before the completion of defoliation. The model sensitivity analysis in the second simulation suggests that a smaller LAI and slower maximum rate of carboxylation likely extend the LDPA because soil water from the surface to rooting depth is maintained longer at levels adequate for carbon gain by decreased canopy transpiration. The experiments also suggest that lower soil hydraulic conductivity and deeper rooting depth can postpone the end of the LDPA by increasing soil water retention and the soil water capacity, respectively.     

Eventual saturation of the climate–carbon cycle feedback studied with a conceptual model

A saturation of climate–carbon cycle feedback was found earlier in the simulations with the IAP RAS climate model of intermediate complexity. Here, this eventual saturation is interpreted by using a conceptual linearised coupled model. It is shown that this saturation is due to weak, logarithmic, dependence of the carbon dioxide radiative forcing on its atmospheric concentration. This eventual saturation leads to the non-monotonic behaviour of climate–carbon cycle parameter f   in time. If the time scale of the atmospheric CO₂${\text{CO}}_2$ build up is _tp$t_{\text{p}}$ then, starting from an initial equilibrium, f   approaches maximum in time ?_tp$?t_{\text{p}}$. Afterwards, climate–carbon cycle parameter decreases and eventually tends to unity. The time scale of the latter decrease is _t1=(1−5)_tp$t_1=(1-5)t_{\text{p}}$. A dependence of _tm$t_{\text{m}}$ and _t1$t_1$ on governing parameters of the conceptual model is studied. It is argued that an eventual saturation of the climate–carbon cycle feedback is expected to occur also in the other integrations of sufficient length with coupled climate–carbon cycle models.     

Electrochemical and optical sensors made of composites of metal–organic frameworks and carbon-based materials. A review

Environmental Chemistry Letters - Rapid and selective sensing of biological substances and pollutants is developing rapidly in medicine and environmental sciences. Sensing performance depends on...     

Migration behavior and in-situ bioremediation of chlorinated hydrocarbon solvent in vadose zone: a review北大核心CSCD

It is of great significance for in-situ bioremediation to clarify the migration behavior and biodegradation laws of chlorinated hydrocarbon solvents (CHS) in the vadose zone. We systematically summarized the phase distribution of CHS, the interaction between different phases, and the migration characteristics and clarified the evolution rules of CHS under different phases in the polluted vadose zone. CHS exists in the vadose zone as the NAPL, dissolved phase, adsorbed phase, gas phase, and other phases, where there are three decay evolution stages: early, middle, and late stages. Phase change and diffusion matrix size are important indicators at different stages; at the same time, gas, solid, liquid and NAPL phase CHS have a variety of interactive relationships in the vadose zone. Subsequently, the characteristics of the three main biological metabolic pathways of CHS in the vadose zone–aerobic co-metabolism, direct oxidation and anaerobic reduction, and dechlorination–and their influencing factors were summarized. Generally speaking, the anaerobic dechlorination capacity decreases with a decrease in the number of chlorine atoms, whereas the aerobic degradation capacity increases with a decrease in the number of chlorine atoms. The current status of in-situ remediation of CHS in the vadose zone was summarized using biostimulation and bioaugmentation methods, indicating that adding nutrient substances and injecting anaerobic dechlorination strains of Dehalococcoides are effective means of remediation. Simultaneously, the factors influencing the biodegradation of CHS in the vadose zone were elaborated to acquire a systematic insight into the significance of redox characteristics (oxygen) on the degradation of CHS. Finally, research on the biodegradation of CHS in the vadose zone is prospected, and it is necessary to carry out research on the interactive relationship between different phases of CHS, the data monitoring of CHS, the structure of the functional bacterial community, and research and development of active strains to provide theoretical guidance for the in-situ remediation of CHS in the vadose zone. © 2022 Science Press. All rights reserved.     

The influence of symbiont type on photosynthetic carbon flux in a model cnidarian–dinoflagellate symbiosis

We measured the relationship between symbiont diversity, nutritional potential, and symbiotic success in the cnidarian–dinoflagellate symbiosis, by infecting aposymbiotic (i.e. symbiont-free) specimens of the model sea anemone Aiptasia sp. with a range of Symbiodinium types. Four cultured heterologous Symbiodinium types (i.e. originally isolated from other host species) were used, plus both cultured and freshly isolated homologous zooxanthellae (i.e. from Aiptasia sp.). Rates of photosynthesis, respiration, and symbiont growth were measured during symbiosis establishment and used to estimate the contribution of the zooxanthellae to the animal’s respiratory carbon demands (CZAR). Anemones containing Symbiodinium B1 (both homologous and heterologous) tended to attain higher CZAR values and hence benefit most from their symbiotic partners. This was despite Symbiodinium B1 not achieving the highest cell densities, though it did grow more quickly during the earliest stages of the infection process. Rather, the heterologous Symbiodinium types A1.4, E2, and F5.1 attained the highest densities, with populations of E2 and F5.1 also exhibiting the highest photosynthetic rates. This apparent success was countered, however, by very high rates of symbiosis respiration that ultimately resulted in lower CZAR values. This study highlights the impact of symbiont type on the functionality and autotrophic potential of the symbiosis. Most interestingly, it suggests that certain heterologous symbionts may behave opportunistically, proliferating rapidly but in a manner that is energetically costly to the host. Such negative host–symbiont interactions may contribute to the host–symbiont specificity seen in cnidarian–dinoflagellate symbioses and potentially limit the potential for partner switching as an adaptive mechanism.     

Assessment of geochemical modeling applications and research hot spots—a year in review

Environmental Geochemistry and Health - Geochemical modeling has been employed in several fields of science and engineering in recent years. This review seeks to provide an overview of case studies...     

China’s sponge cities alleviate urban flooding and water shortage: a review

Environmental Chemistry Letters - About one tenth of humans are impacted by water shortages around the globe. Water resilience is worsening under climate change because intensifying weather...     

Major and trace elements in paddy soil contaminated by Pb–Zn mining: a case study of Kočani Field,Macedonia

The objective of this study was to assess the bulk chemical composition as well as the extent and severity of heavy metal contamination in the paddy soil of Kočani Field (eastern Macedonia). The results revealed that the paddy soil of the western part of Kočani Field is severely contaminated with Pb, Zn, As and Cd in the vicinity of the Zletovska River due to irrigation with riverine water that is severely affected by acid mine and tailing effluents from the Pb–Zn mine in Zletovo. The detected total concentrations of these metals are far above the threshold values considered to be phytotoxically excessive for surface soil. The paddy soil in the vicinity of the Zletovska River was also found to exhibit elevated levels of Ba, Th, U, V, W, Mo, Cu, Sb, Bi, Ag, Au, Hg and Tl, with concentrations above their generally accepted median concentration values obtained during this study. A correlation matrix revealed that the Mn and Fe oxides/hydroxides are the most important carrier phase for several trace elements, with the exception of rare earth elements (REEs). These also represent a major sink for the observed heavy metal pollution of the soil. REEs are mostly associated with two phases: light (L)REEs are bound to K-Al, while heavy (H)REEs are bound to Mg-bearing minerals. Although there is no direct evidence of a health risk, the paddy soil in the vicinity of Zletovska River needs further investigation and an assessment should be made of its suitability for agricultural use, particularly in view of the highly elevated concentrations of Pb, Zn, As and Cd.     

Carbon dioxide use by chemoautotrophic endosymbionts of hydrothermal vent vestimentiferans: affinities for carbon dioxide, absence of carboxysomes, and δ13C values

The hydrothermal vent vestimentiferans Riftia pachyptila Jones, 1981 and Ridgeia piscesae Jones, 1985 live in habitats with different abundances of external CO₂. R. pachyptila is found in areas with a high input of hydrothermal fluid, and therefore with a high [CO₂]. R. piscesae is found in a range of habitats with low to high levels of hydrothermal fluid input, with a correspondingly broad range of CO₂ concentrations. We examined the strategies for dissolved inorganic carbon (DIC) use by the symbionts from these two species. R. pachyptila were collected from the East Pacific Rise (9°50′N; 104°20′W) in March 1996, and R. piscesae were collected from the Juan de Fuca Ridge (47°57′N; 129°07′W) during September of 1996 and 1997. The differences in the hosts' habitats were reflected by the internal pools of DIC in these organisms. The concentrations of DIC in coelomic fluid from R. piscesae were 3.1 to 10.5 mM, lower than those previously reported for R. pachyptila, which often exceed 30 mM. When symbionts from both hosts were incubated at in situ pressures, their carbon fixation rates increased with the extracellular concentration of CO₂, and not HCO₃ ⁻, and symbionts from R. piscesae had a higher affinity for CO₂ than those from R. pachyptila (K _1/2 of 7.6 μM versus 49 μM). Transmission electron micrographs showed that symbionts from R. piscesae lack carboxysomes, irrespective of the coelomic fluid [DIC] of their host. This suggests that the higher affinity for CO₂ of R. piscesae symbionts may be their sole means of compensating for lower DIC concentrations. The δ¹³C values of tissues from R. piscesae with higher [DIC] in the coelomic fluid were more positive, opposite to the trend previously described for other autotrophs. Factors which may contribute to this trend are discussed. Received: 24 September 1998 / Accepted: 12 May 1999     

Biogeochemical transfer and dynamics of iodine in a soil–plant system

Radioactive iodide (¹²⁵I) is used as a tracer to investigate the fate and transport of iodine in soil under various leaching conditions as well as the dynamic transfer in a soil–plant (Chinese cabbage) system. Results show that both soils (the paddy soil and the sandy soil) exhibit strong retention capability, with the paddy soil being slightly stronger. Most iodine is retained by soils, especially in the top 10 cm, and the highest concentration occurs at the top most section of the soil columns. Leaching with 1–2 pore volume water does not change this pattern of vertical distributions. Early breakthrough and long tailing are two features observed in the leaching experiments. Because of the relatively low peak concentration, the early breakthrough is really not an environmental concern of contamination to groundwater. The long tailing implies that the retained iodine is undergoing slow but steady release and the soils can provide a low but stable level of mobile iodine after a short period. The enrichment factors of ¹²⁵I in different plant tissues are ranked as: root > stem > petiole > leaf, and the ¹²⁵I distribution in the young leaves is obviously higher than that in the old ones. The concentrations of ¹²⁵I in soil and Chinese cabbage can be simulated with a dual-chamber model very well. The biogeochemical behaviors of iodine in the soil-cabbage system show that cultivating iodized cabbage is an environmentally friendly and effective technique to eliminate iodine deficiency disorders (IDD). Planting vegetables such as cabbage on the ¹²⁹I-contaminated soil could be a good remediation technique worthy of consideration.     

Tests for aggregated dispersion: Van Valen’s test and a new competitor

Environmental and Ecological Statistics - Van Valen’s test is usually applied as a two sample test for equality of dispersion for multivariate data. Motivated by a comment of Manly (Van...     

Exploring thermal and trophic preference of Balaenoptera physalus in the central Tyrrhenian Sea: a new summer feeding ground?

In the 1990s, the central Tyrrhenian Sea was regarded as a transit region for fin whales’ (Balaenoptera physalus) summer migration. In recent years, a much higher presence of fin whales during the entire summer season was reported in the region. The hypothesis that the central Tyrrhenian Sea may have become a summer feeding ground was tested gathering data from summer presence of whales in the region (40–42.5°N; 9–13°E) and investigating whether it might be related to sea surface temperature and chlorophyll-a concentration, considered as proxies of food availability. Results showed that whales always aggregate in the more productive portions of the investigated area; the general productivity of the area, however, did not directly influence the frequency of occurrence of whales. We concluded that the complex dynamics of the balance between feeding activities and avoiding pressures may have led fin whales to use the region as an opportunistic feeding ground.     

Light and carbon balance in the seagrass Thalassia testudinum : evaluation of current production models

The production dynamics and carbon balance of Thalassia testudinum in the lower Laguna Madre, Texas, USA, were examined during the 1995 summer period based on in situ photosynthesis vs irradiance (PI) measurements and continuous measurements of underwater photon-flux density (PFD). The validity of applying the H _sat model, used to calculate production for Zostera marina as the product of the maximum rate of photosynthesis (P _max) and daily hours of saturating irradiance (H _sat) was assessed for T. testudinum by comparison with integrated production estimates derived through numerical integration. Gross integrated production values were combined with dark-respiration measurements of photosynthetic (PS) and non-photosynthetic (NPS) tissues and areal biomass to generate daily whole-plant carbon balance. Production and whole-plant carbon balance are discussed in relation to surface and underwater PFD measurements, biomass and other physical and chemical parameters collected during a 1 yr period from January to December 1995. The H _sat model significantly underestimated production during all summer months, averaging 70% of integrated production over the entire study period. Gross integrated production ranged between 11.5 mg C g⁻¹ leaf dry wt d⁻¹ in June (during a period of unseasonably low PFDs caused by a drift-alga mat covering the seagrass bed) to 26.7 mg C g⁻¹ leaf dry wt d⁻¹ in July. Modeled net carbon gain was highest in July at 454 mg C m⁻² d⁻¹ (1.4 g dry wt m⁻² d⁻¹), sufficient to account for measured rates of leaf production in the study area and representative of T. testudinum populations of low productivity. During part of the summer period, however, the population was in negative carbon balance. The relatively low productivity of this population and the periods of negative carbon balance are attributed to low net photosynthesis:dark respiration (P _net:R _d) ratios, sporadic low-light periods, the small fraction of PS tissue relative to whole-plant biomass (5 to 13%) and nutrient limitation. Production models are sensitive to both light availability and the proportion of PS tissue supporting NPS biomass as reflected in whole-plant P _net:R _d ratios. Received: 13 August 1997 / Accepted: 6 March 1998     

Atypical plant–herbivore association of algal food and a kleptoplastic sea slug (Elysia clarki) revealed by DNA barcoding and field surveys

The identity of food sources and feeding preferences of specialist herbivores have been commonly inferred from spatial associations between consumer and food items. However, such basic information for well-known marine herbivores, sacoglossans (sea slugs), and their algal diets remains disappointingly lacking, especially from field studies. The sacoglossan, Elysia clarki (Pierce et al. in Molluscan Res 26:23–38, 2006), is kleptoplastic and sequesters chloroplasts from algal food to photosynthesize, so DNA identification of sequestered chloroplasts was employed to verify the algal species fed upon by the slug across its geographic range. The molecular information on the algae consumed by E. clarki was combined with field surveys of slugs and algae in slug habitats in the Florida Keys in July and August of 2008 in order to evaluate whether the diet of this herbivore could be predicted based on its spatial association with algae in the field. A considerable mismatch between food availability and kleptoplast identity was recorded. E. clarki commonly occupied areas devoid of potential food and often contained symbiotic plastids from algal species different from those most frequently found in the surveyed habitats. In three of the four study sites, algal species present were poor predictors of slug diet. These findings suggest that the photosynthetic capability of E. clarki may release the slug from the constraint of requiring proximity to its food sources and may allow for the potential lack of spatial coupling between this herbivore and its algal food. This combination of field surveys and DNA barcoding provided critical and previously unavailable information on herbivore feeding in this marine system.     

Using adsorption and sulphide precipitation as the principal removal mechanisms of arsenic from a constructed wetland – a critical review

This review has been undertaken to understand the role of various parameters such as redox potential, microbes, and organic matters on the fate and transport of arsenic in the constructed wetland. A conceptual diagram of arsenic fate and transport in the constructed wetland was developed. Role of various minerals which are produced due to microbial activities are described. The role of these minerals on arsenic adsorption is discussed. It was envisaged that iron sulphide would be the main adsorbent for arsenic in microbe-mediated adsorption process. Beside microbe-mediated arsenic adsorption, roles of various microbes, such as sulphate reducers and methane producers, on arsenic transformation are discussed. Role of various organic carbon sources and electron acceptors on the proliferation of the above mentioned microbes with respect to arsenic transformation was envisaged. Role of dissolved organic matters on arsenic transformation and transport was also discussed in details. To strengthen the review, laboratory studies and modelling of arsenic adsorption and transformation using the Visual Minteq were appended.