Catalyst-free synthesis of α-acyloxycarboxamides in aqueous media

Environmental Chemistry Letters - Organic syntheses in aqueous solutions are being developed because water is an environmentally friendly, inexpensive, non-toxic and non-flammable solvent....     

Role of methoxy and Cα-based substituents in electrochemical oxidation mechanisms and bond cleavage selectivity of β-O-4 lignin model compounds

In order to better understand the specific substituent effects on the electrochemical oxidation process of β-O-4 bond, a series of methoxyphenyl type β-O-4 dimer model compounds with different localized methoxyl groups, including 2-(2-methoxyphenoxy)-1-phenylethanone, 2-(2-methoxyphenoxy)-1-phenylethanol, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2-methoxyphenoxy)-1-(4-methoxyphenyl)ethanol, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphenyl)ethanone, 2-(2,6-dimethoxyphenoxy)-1-(4-methoxyphe...     

Interrelation of Cd‐lon concentrations and the growth and activities of microorganisms in two growth media†

Partitioning of native or anthropogenic heavy metals in solid and solution phases of soil is a result of network of several physico‐chemical reactions. The attainment of equilibrium between two phases is also regulated by biochemical processes. For practical purposes, the bioavailability of metal present in soil is predominantly regulated by the soil solution phase which is in dynamic equilibrium with the solid phase. The results of a model laboratory and greenhouse growth experiments have been used to investigate the effect of Cd‐ion concentrations (either in soil solution or in nutrient solution) on the growth and activities of microorganisms. The soil solution has been simulated by preparing a suspension of soil with 0.1 M NaNO₃ (1: 2.5) equilibrated for two hours. Important conclusions are as follows:

Increase in Cd‐ion concentration in soil solution or in nutrient solution induces corresponding adverse effect on the growth and activities of microorganisms. Thus, it seems that Cd‐ion concentration is a more sensitive indicator for assessing the effect of metal pollution upon the growth and activities of soil microorganisms in comparison to total Cd contents.

During active microbial growth phase, a large part of the organically bound Cd was released in the soil solution which is largely bioavailable. This process is termed as mobilisation. There was momentary increase of Cd‐ion concentration in soil solution which intoxicated the growing organisms. After this stage, the Cd ions from the solution phase were removed by the newly formed solid phase (nonviable biomass) and were transformed in non‐available form. This process is termed as immobilisation.

The consequences and importance of these results for practical agriculture and in deciding the limits or guidelines on the maximum tolerable metal load in soils are discussed.     

Quantity and activity of ammonia-oxidizing archaea and bacteria and their contribution to ammonia oxidation in farmland soil of Qinghai-Tibet Plateau北大核心CSCD

Ammonia oxidation, the first and rate-limiting step of nitrification, is mainly performed by ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB). However, the activities of AOA and AOB in soil and their relative contribution to ammonia oxidation are unclear, and whether there is a significant correlation between the quantity of AOA and AOB and the ammonia oxidation rate is also controversial. In this study, quantitative PCR combined with acetylene (C2H2) and 1-octyne inhibition methods were used to determine the quantity and activity of AOA and AOB in wheat, highland barley, and oilseed rape soils in Nyingchi, Lhatse, Sangzhuzi, and Sangri counties on the Qinghai-Tibet Plateau. The results showed that the quantity of AOB ((2.34 ± 0.84) ×105 - (2.65 ± 1.07) ×106 copies g-1 dry soil) was significantly higher than that of AOA ((0.20 ± 0.10) ×104 - (4.02 ± 0.39) ×104 copies g-1 dry soil) in all the soil samples. Soil pH was the key factor affecting the quantity of AOB, and the total phosphorus and ammonium nitrogen in soil were the key factors affecting the quantity of AOA. The rates of ammonia oxidation in the farmland soils of Lhatse (2.42 ± 0.73 mg kg-1 d-1) and Sangzhuzi (3.24 ± 1.15 mg kg-1 d-1) were significantly higher than those in the soils of Nyingchi (1.17 ± 0.43 mg kg-1 d-1) and Sangri counties (0.88 ± 0.57 mg kg-1 d-1). The rates of ammonia oxidation in the farmland soils of Lhatse and Sangzhuzi were dominated by AOB, while those in the farmland soils of Nyingchi and Sangri counties were dominated by AOA. For crops, the ammonia oxidation rates of wheat and oilseed rape soils in all four regions were significantly higher than those of highland barley soil, whereas the activity of AOA and AOB was not influenced by crops. The ratio of nitrogen to phosphorus was the key factor influencing AOA activity, whereas soil pH and total carbon were the main factors influencing AOB activity. Additionally, the quantities of AOA and AOB were not significantly correlated with the total ammonia oxidation rates and AOA and AOB activity. Overall, our study suggests that both AOA and AOB play important roles in ammonia oxidation in farmland soils of the Qinghai-Tibet Plateau. Moreover, it is unreliable to predict the activity of AOA and AOB and their relative contribution to ammonia oxidation directly based on their number of amoA genes, and the activity of AOA and AOB should be directly and accurately measured. These results are important for understanding ammonia nitrogen removal processes, slowing nitrate loss, and reducing the emission of the greenhouse gas nitrous oxide in the farmland ecosystem of the Qinghai-Tibet Plateau. © 2022 Science Press. All rights reserved.     

Catalytic ozonation of reactive red X-3B in aqueous solution under low pressure: decolorization and OH· generation

Catalytic ozonation of Reactive Red X-3B in aqueous solution had been carried out in an ozone oxidation reactor where Mn-Fe-ceramic honeycomb was used as the catalysts. The presence of Mn-Fe-ceramic honeycomb catalyst could obviously improve the decoloration efficiency of Reactive Red X-3B and the utilization efficiency of ozone compared to the results from non-catalytic ozonation. Adsorption of Reactive Red X-3B had no obviously influence on the degradation efficiency. Addition of tert-butanol significantly decreased the degradation efficiency, indicating that the degradation of Reactive Red X-3B followed the mechanism of hydroxyl radical (OH·) oxidation. The operating variables such as reaction pressure and ozone supply had a positive influence on the degradation efficiency, mainly attributing to facilitate the ozone decomposition and OH· formation.     

Stability studies of cholesterol lowering statin drugs in aqueous samples using HPLC and LC–MS

In this study, stability of statin drugs in different conditions, such as various pH, diverse solvents ratio, presence of UV, and sunlight have been investigated. Results suggest strong dependence of statins upon pH, potential environmental persistence towards sun light, and UV light degradation via singlet excited state obtained by excitation into the π–π* band. In acidic conditions interconversion between lactone and hydroxy acid forms in aqueous solutions at room temperature is retarded, while for the same sun-exposed samples are accelerated. Longer exposures lead to the degradation processes. Statin interconversion in water is much lower than in acetonitrile.     

Use of one-dimensional modelling in estuary management: entrance depth –– model calibration

The Wairoa River, a barrier enclosed estuary situated in Hawke’s Bay, New Zealand was modelled using a one-dimensional hydrodynamic model. Water level data obtained during a flood and a bathymetric survey were available but the entrance cross-section had not been surveyed. This paper describes the calibration of the model to jointly optimise the selection of the Manning coefficient and the depth of the estuary entrance.     

Photolytical property of L(+)-α-phenylglycine in aqueous solution

A wide range of pharmaceutical compounds have been identified in the environment, and their existence is a topic of growing concern, both for human and ecological health. The work described here has investigated the photolytic properties of L(+)-α-phenylglycine (L-α-PG-H) in aqueous solution as it can be degraded by photo-catalysis. In 266 nm laser flash photolysis of aqueous solution of L-α-PG-H saturated with nitrogen, two transient absorption bands are observed at 280–330 nm and 450–800 nm, respectively, due to L-α-PG-H radical cation and hydrated electrons (e_aq⁻). Then e_aq⁻ reacts with L-α-PG-H to form the L-α-PG-H radical anion. Decaying rate constants of e_aq⁻ observed at 720 nm is to be 8.9 × 10⁸ dm³ mol⁻¹ s⁻¹. The rate constant for oxidation of L-α-PG-H by SO₄ ⁻ is calculated as 4.5 × 10⁸ and 4.3 × 10⁸ s⁻¹ mol⁻¹ dm³, respectively. The dissociation constants (pKa) of L-α-PG-H is 3. Excited triplet of L-α-PG-H in solution is formed by laser flash photolysis. The quench rate constant of L-α-PG-H excited triplet (k _s) is determined to be 1.3 × 10⁷ dm³ mol⁻¹ s⁻¹ and k ₀ is equal to 1.7 × 10⁵ s⁻¹.     

Genotoxic consequences of occupational exposure to ethylene oxide and formaldehyde ‐ a pilot study

The study evaluates chromosome damage caused by simultaneous occupational exposure to ethylene oxide (EtO) and formaldehyde (FA). To determine the extent of chromosome damage, eleven workers were analyzed using chromosome aberration (CA) assay, sister chromatid exchange (SCE) frequencies, micronucleus (MN) assay, and mitotic activity (MA). The results show significant deviations in subjects exposed to EtO and FA from control values in all four assays. The study shows a complex mode of action of EtO and FA on human genome and confirms the need for further research of cytogenetic risk which should be obtained through several assays.     

Recent advances in activity inhibition,recovery and enhancement,and application of the anaerobic ammonium oxidation process北大核心CSCD

Anaerobic ammonium oxidation (Anammox) is a biological process that has the advantages of saving energy and being highly efficient. However, there are some problems with it such as slow proliferation and activity inhibition of Anammox bacteria in practical applications. First, we introduce the inhibitory effects of Anammox by substrate and non-substrate materials, including nitrite, organic and inorganic substances, and others, and elaborated on activity recovery approaches such as controlling the operation parameters and adding sludge. The effects of the addition of inorganic carbon, Anammox intermediates, Fe, and conductive materials on Anammox are then reviewed in detail, and three Anammox metabolic pathways are summarized. Finally, we discuss the problems (including NOB inhibition and low temperature) and countermeasures when Anammox is applied for wastewater treatment as a mainstream technology, and we summarized the measures of NOB washout by free ammonia and free nitrite solutions and methods to cope with low temperatures, including selecting suitable reactor types and culture methods. Meanwhile, we analyzed the interactions among the intermediates and the synergy between Anammox and denitrification and suggest the potential of applying Anammox for flue gas denitrification and anaerobic aromatic hydrocarbon biodegradation. Further studies are suggested regarding multifactor composite inhibition, Anammox physiological characteristics, and intermediate metabolic mechanisms as well as regarding methods for avoiding adverse factors in mainstream wastewater treatment. © 2018 Science Press. All rights reserved.     

Performance and validation of a coupled parallel ADCIRC–SWAN model for THANE cyclone in the Bay of Bengal

An accurate prediction of near-shore sea-state is imperative during extreme events such as cyclones required in an operational centre. The mutual interaction between physical processes such as tides, waves and currents determine the physical environment for any coastal region, and hence the need of a parallelized coupled wave and hydrodynamic model. The present study is an application of various state-of-art models such as WRF, WAM, SWAN and ADCIRC used to couple and simulate a severe cyclonic storm Thane that developed in the Bay of Bengal during December 2011. The coupled model (ADCIRC–SWAN) was run in a parallel mode on a flexible unstructured mesh. Thane had its landfall on 30 December, 2011 between Cuddalore and Pondicherry where in-situ observations were available to validate model performance. Comprehensive experiment on the impact of meteorological forcing parameters with two forecasted tracks derived from WRF model, and JTWC best track on the overall performance of coupled model was assessed. Further an extensive validation experiment was performed for significant wave heights and surface currents during Thane event. The significant wave heights measured along satellite tracks by three satellites viz; ENVISAT, JASON-1 and JASON-2, as well in-situ near-shore buoy observation off Pondicherry was used for comparison with model results. In addition, qualitative validation was performed for model computed currents with HF Radar Observation off Cuddalore during Thane event. The importance of WRF atmospheric model during cyclones and its robustness in the coupled model performance is highlighted. This study signifies the importance of coupled parallel ADCIRC–SWAN model for operational needs during extreme events in the North Indian Ocean.     

Bioaccumulation and adverse effects of trace metals and polycyclic aromatic hydrocarbons in the common onion Allium cepa as a model in ecotoxicological bioassays

The common onion Allium cepa can be easily used in ecotoxicological bioassays to evaluate the bioavailability and adverse effects of pollutants and complex mixtures like waste, industrial effluent or coal-mining drainage that contain elevated levels of trace metals and polycyclic aromatic hydrocarbons (PAHs). In this study, onions were exposed for 7 days to individual metals (1?µg?mL^?1), i.e., aluminium, copper, iron and manganese, or PAHs (1.5?ng?mL^?1), i.e., benzo[a]antracene and benzo[a]pirene. Biological effects, measured as growth inhibition of roots and leaves, were integrated with analysis of bioaccumulation in roots, bulbs and leaves. Copper, iron and benzo[a]pirene caused a significant inhibition in root development of newly formed tissues, whereas only slight variations were caused by other chemicals; the number of new root filaments and the length of the leaves did not show significant variations, thus not representing sensitive parameters to evaluate adverse effects of pollutants in A. cepa. Chemicals bioaccumulation was always significant in roots, whereas levels in bulbs and leaves exhibited increased levels only for manganese, and a decrease for aluminium. The overall results confirmed the sensitivity of the bioassays with A. cepa, suggesting their utility for future applications to evaluate the adverse effects of complex mixtures containing metals or PAHs.     

Pb,Cd, Zn and cu intakes of Taiwanese subjects ‐ a duplicate portion study

Thirty diet samples from three different social groups were collected both in summer and in winter seasons using duplicate portion technique with three collection days. Toxic element concentrations, including Pb, Cd, as well as some essential elements were determined by atomic absorption spectrometry (AAS). The average dietary intakes of Taiwanese were estimated as follows (means ± S.D., n = 30): Mg, 175 ± 77 mg/day; Zn, 9.5 ± 11.4 mg/day; Mn, 2.8 ± 1.3 mg/day; Cu, 1.6±1.7mg/day; Ni, 0.13 ± 0.14 mg/day; Cd, 58 ± 62 μg/day, and Pb, 31 ±26 μg/day. The obtained elemental concentrations were scattered due to different dietary habits and cooking methods. In addition, a strong correlation arose between the trace element concentrations in agricultural products and in the diet of regional areas of Taiwan. Analysis results indicated that average intakes are consistently below current US Recommended Daily Allowances (RDAs) for Mg and Zn, within the recommended safe and adequate RDA for Mn, and below the FAO/WHO Provisional Tolerable Daily Intakes (PTDIs) for Pb. The average daily intakes of Cd by regional area of Taiwan markedly exceeded those of other countries and the PTI value during the summer.     

Preparation and characterization of β-FeOOH-coated sand and its adsorption of Cr(VI) from aqueous solutions

Batch adsorption experiments were conducted to explore the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand. We investigated the key factors which affected the adsorption process such as adsorbent dosage, initial pH, initial Cr(VI) ion concentration, contact time and temperature. The uptake of Cr(VI) was very rapid and 44.3%, 51.6%, 58.9% of the adsorption happened during the first 180 minutes at 293K, 303K and 313K, respectively. The pseudo-second-order rate equation successfully described the adsorption kinetics. To study the adsorption isotherm, two equilibrium models, the Langmuir and Freundlich isotherms, were adopted. At 293K, 303K and 313K, the adsorption capacities obtained from the Langmuir isotherm were 0.060, 0.070 and 0.076 mg Cr(VI) per gram of the adsorbent, respectively. Thermodynamic parameters such as the change of energy, enthalpy and entropy were calculated using the equilibrium constants. The negative value of ΔG0 and the positive value of ΔH0 showed that the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand was spontaneous, endothermic and occurred by physisorption.     

Exploring human–nature interactions in national parks with social media photographs and computer vision

Understanding the activities and preferences of visitors is crucial for managing protected areas and planning conservation strategies. Conservation culturomics promotes the use of user-generated online content in conservation science. Geotagged social media content is a unique source of in situ information on human presence and activities in nature. Photographs posted on social media platforms are a promising source of information, but analyzing large volumes of photographs manually remains laborious. We examined the application of state-of-the-art computer-vision methods to studying human–nature interactions. We used semantic clustering, scene classification, and object detection to automatically analyze photographs taken in Finnish national parks by domestic and international visitors. Our results showed that human–nature interactions can be extracted from user-generated photographs with computer vision. The different methods complemented each other by revealing broad visual themes related to level of the data set, landscape photogeneity, and human activities. Geotagged photographs revealed distinct regional profiles for national parks (e.g., preferences in landscapes and activities), which are potentially useful in park management. Photographic content differed between domestic and international visitors, which indicates differences in activities and preferences. Information extracted automatically from photographs can help identify preferences among diverse visitor groups, which can be used to create profiles of national parks for conservation marketing and to support conservation strategies that rely on public acceptance. The application of computer-vision methods to automatic content analysis of photographs should be explored further in conservation culturomics, particularly in combination with rich metadata available on social media platforms.     

Up to 95 % reduction of chemical oxygen demand of slaughterhouse effluents using Fenton and photo-Fenton oxidation

Meat industries produce effluents containing high concentrations of organic and inorganic compounds, which must be removed before being discharged or reused. Advanced oxidation processes using Fenton reaction coupled with UV, solar radiation, and electrochemical oxidation are promising methods. Here, we treated the effluent from an anaerobic digester using: (a) the photoelectro-Fenton process, using a system with a Ti-RuO₂ anode and a carbon felt cathode, (b) the solar photo-Fenton process, using a batch reactor and a compound parabolic collector, and (c) a combination of Fenton and solar photo-Fenton processes. The effluent had an initial chemical oxygen demand (COD) of 1159 mgL^?1, and we obtained high removal efficiencies of COD, up to 95 %, using the combination of Fenton and solar photo-Fenton processes.     

Sensitivity of a coupled physical–biological model to turbulence: high-frequency simulations in a northern Adriatic station

This paper investigates the impacts of different turbulence models on the biological state at an ocean station in the northern Adriatic sea, named S3, comparing them with other uncertainties inherent to coupled physical–biological simulations. The numerical tool is a 1-D model resulting from the coupling of two advanced numerical models. The hydrodynamic part is modelled using the General Ocean Turbulence Model (www.gotm.net), in a version adopting state-of-the-art second-moment Turbulence Closure Models (TCMs). Marine biogeochemistry is parameterized with the Biogeochemical Flux Model (http://www.bo.ingv.it/bfm), which is a direct descendant of ERSEM (European Regional Sea Ecosystem Model). Results, obtained by forcing the model with hourly wind and solar radiation data and assimilating salinity casts, are compared against monthly observations made at the station during 2000–2001. Provided that modern second-moment TCMs are employed, the comparisons indicate that both the physical and the biological dynamics are relatively insensitive to the choice of the particular scheme adopted, suggesting that TCMs have finally ‘converged’ in recent years. As a further example, the choice of the nutrient boundary conditions has an impact on the system evolution that is more significant than the choice of the specific TCM, therefore representing a possible limitation of the 1-D model applied to stations located in a Region of Freshwater Influence. The 1-D model simulates the onset and intensity of the spring–summer bloom quite well, although the duration of the bloom is not as prolonged as in the data. Since local dynamics appears unable to sustain the bloom conditions well into summer, phytoplankton at the station was most likely influenced by river input or advection processes, an aspect that was not found when the S3 behaviour was adequately modelled using climatological forcings. When the focus is in predicting high-frequency dynamics, it is more likely that lateral advection cannot be neglected. While the physical state can be satisfactorily estimated at these short time scales, the accurate estimation of the biological state in coastal regions still appears as rather elusive.     

Direct use values of communal resources in Bokong and Tsehlanyane in Lesotho: whither the commons?

SUMMARY

This paper presents a comprehensive assessment of the contribution of communal resources to households in Bokong and Tsehlanyane in Lesotho. It argues that communal resources are an extremely important element in the livelihoods of people in the study area. It uses households as units of analysis in order to gain an understanding of the role that communal resources play at the micro level before any extrapolations are made to the regional and national levels. A household survey, guided by a detailed semistructured questionnaire, was used. Ten newly constructed houses and vegetable garden enclosures were sampled to categorize and count all poles used to build them. The amount of thatch grass used in building those houses was also estimated. The results indicated that communal resources play a central role in the livelihoods of people in the area with firewood ($1492), crops ($1363) and wild vegetables ($774) recording the highest annual use values per household^?1 yr^?1. The total present value was estimated at $3899 household^?1 yr^?1 with firewood, crops and wild vegetables constituting 93% of that value. The study further demonstrated that communal resources are used across the entire income spread in the area, thereby negating the general belief that they are a preserve of the poor. Finally, the results demonstrated that very little value is derived through trading of resources both within and outside the area but through direct consumption within households invariably escaping national economic accounting. With declining employment rates in Lesotho due to continued retrenchments in the South African mining industry, communal resources in the country remain an indispensable resource that must be carefully managed for the common good.     

Absorption and retention of polydimethylsiloxanes (silicones) in fish: Preliminary experiments†

Hydrophobicity and bioaccumulation potential of linear and cyclic polydimethylsiloxane (PDMS) oligomers were estimated by reversed‐phase liquid chromatography and feeding experiments with guppies (Poecilia reticulata). PDMS concentrations in fish were determined by capillary column gas chromatography and gas chromatography‐mass spectrometry. In contrast to polychlorinated biphenyls (PCBs), only very small amounts of PDMS were retained by the fish after six weeks feeding.     

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.