Machine-learning paradigms for selecting ecologically significant input variables

Harmful algal blooms, which are considered a serious environmental problem nowadays, occur in coastal waters in many parts of the world. They cause acute ecological damage and ensuing economic losses, due to fish kills and shellfish poisoning as well as public health threats posed by toxic blooms. Recently, data-driven models including machine-learning (ML) techniques have been employed to mimic dynamics of algal blooms. One of the most important steps in the application of a ML technique is the selection of significant model input variables. In the present paper, we use two extensively used ML techniques, artificial neural networks (ANN) and genetic programming (GP) for selecting the significant input variables. The efficacy of these techniques is first demonstrated on a test problem with known dependence and then they are applied to a real-world case study of water quality data from Tolo Harbour, Hong Kong. These ML techniques overcome some of the limitations of the currently used techniques for input variable selection, a review of which is also presented. The interpretation of the weights of the trained ANN and the GP evolved equations demonstrate their ability to identify the ecologically significant variables precisely. The significant variables suggested by the ML techniques also indicate chlorophyll-a (Chl-a) itself to be the most significant input in predicting the algal blooms, suggesting an auto-regressive nature or persistence in the algal bloom dynamics, which may be related to the long flushing time in the semi-enclosed coastal waters. The study also confirms the previous understanding that the algal blooms in coastal waters of Hong Kong often occur with a life cycle of the order of 1–2 weeks.     

Surface acidity study of Mn+-montmorillonite clay catalysts by FT-IR spectroscopy: Correlation with esterification activity

A simple method for evaluating the surface acidity of different cation-exchanged montmorillonite (mont) clay catalysts, Mⁿ⁺-mont (Mⁿ⁺=Al³⁺, Fe³⁺, Cr³⁺, Zn²⁺, Ni²⁺, Cu²⁺, and H⁺), involving treatment with pyridine is described. After treating with pyridine, the samples were heated at 120 °C and the FT-IR spectra were directly recorded in the region 1650 and 1350 cm⁻¹. The data obtained show the presence of both Lewis and Brønsted acid sites. The activities of the catalysts to bring about Brønsted acid catalysed esterification of succinic acid with iso-butanol to yield di-(iso-butyl) succinate have been studied. The Brønsted acidity data obtained for Mⁿ⁺-mont correlated well with activity in the esterification reaction. The activities of the catalysts were found to decrease in the order of exchange ions Al³⁺ > Fe³⁺ > Cr³⁺ > Zn²⁺ > Ni²⁺ > Cu²⁺ > Na⁺-mont. They also correlated well with the charge to radius ratio of the cations. The catalysts exchanged with trivalent cations showed stronger absorption bands attributed to Brønsted acidity (1540 cm⁻¹) whereas those exchanged with divalent cations showed an increased Lewis acidity (1450 cm⁻¹) and reduced Brønsted acidity along with charge to radius ratio. Zn²⁺-, Cu²⁺- and Ni²⁺-exchanged clays showed an additional peak around 1605 cm⁻¹ which is attributed to the pyridine adsorption on surface sites through its π electrons. The method suggested here to evaluate the acidity is suitable for active sites which are thermally unstable such as water molecules in the hydration shell of a cation in exchanged clay.     

Synthesis,structure, and adsorption properties of a three-dimensional porous yttrium–organic coordination network

Deprotonation of 4,4′-biphenyldicarboxylic acid (H₂BPDC) with triethylamine followed by the copolymerization with Y(III) in N,N-dimethylformamide (DMF) at room temperature yields a new three-dimensional (3-D) porous metal–organic coordination network, [Y₂(BPDC)₃(DMF)₂(H₂O)₂]_n · (DMF)_n · (H₂O)_n (1). Compound 1 (C_24.50H₁₉N_1.50O₉Y) crystallizes in the triclinic P-1 space group (a = 8.220 (2), b = 13.998 (4), c = 14.212 (4) Å, α = 111.058 (5)°, β = 90.187 (5)°, γ = 94.318 (5)°, V = 1520.9 (7) ų, and Z = 2). X-ray crystallography reveals that 1 consists of a 3-D framework contained open 1-D channels with the dimension of 5 × 10 Å along the crystallographic a axis. The adsorption measurements show that compound 1 can adsorb N₂, Ar and CO₂ into its pores. The adsorption isotherms for MeOH and H₂O were also measured.     

溴酸根在紫外和氯消毒联用工艺中的形成

以H2O-Br--Cl2/NH2Cl/ClO2为研究对象,考查UV作用下BrO3-产生的情况。结果表明：原水和去离子水背景下,Cl2/UVC联用可以氧化部分的Br-生成BrO3-;NH3可以有效的抑制BrO3-生成,并且NH2Cl/UVC作用时不生成BrO3-;ClO2/UV体系产生溴酸根能力明显弱于Cl2/UV;ClO2/UVC产生BrO3-的量高于ClO2/UVA。酸性条件同时促进BrO3-的产生和ClO2的分解,碱性条件正好相反。     

生物硅藻土-动态膜生物反应器处理微污染原水的研究

以硅藻土作为基材开发了一种新型给水处理技术——生物硅藻土-动态膜反应器,并对该工艺系统处理微污染原水的去除性能进行了小试研究.结果表明,在通量为40 L/(m2.h)的条件下,系统对浊度有较好的去除效果,且出水浊度均在1 NTU以下.本工艺对CODMn和UV254也有较好的去除效果,去除率分别达58.14%和45.8%,这主要是由于硅藻土吸附、微生物降解和动态膜的分离作用;同时,反应器对氨氮的去除率也较好,达到90%以上,这主要基于反应器内微生物的分解作用.     

Understanding Boosted Selective CO2-to-CO Photoreduction with Pure Water Vapor over Hierarchical Biomass-Derived Carbon Matrix

Solar-driven CO₂ reduction reaction (CO₂RR) with water into carbon-neutral fuels is of great significance but remains challenging due to thermodynamic stability and kinetic inertness of CO₂. Biomass-derived nitrogen-doped carbon (N-C_b) have been considered as promising earth-abundant photocatalysts for CO₂RR, although their activities are not ideal and the reaction mechanism is still unclear. Herein, an efficient catalyst is developed for CO₂-to-CO conversion realized on diverse N-C_b materials with hierarchical pore structures. It is demonstrated that the CO₂-to-CO conversion preferentially takes place on positively charged carbon atoms next to pyridinic-N using two representatives treated pollens with the largest difference in pyridinic-N density and N content as model photocatalysts. Systematic experimental results indicate that surface local electric field originating from charge separation can be boosted by hierarchical pore structures, doped N, as well as pyridinic-N. Mechanistic studies reveal that positively charged carbon atoms next to pyridinic-N serve as active sites for CO₂RR, reduce the energy barrier on the formation of CO*, and facilitate the CO₂RR performance. All these benefits cooperatively contribute to treated chrysanthemum pollen catalyst exhibiting excellent CO formation rate of 203.2 µmol h⁻¹ g⁻¹ with 97.2% selectivity in pure water vapor. These results provide a new perspective into CO₂RR on N-C_b, which shall guide the design of nature-based photocatalysts for high-performance solar-fuel generation.     

Hydration characteristics of municipal solid waste incinerator bottom ash slag as a pozzolanic material for use in cement

This study investigated the pozzolonic reactions and engineering properties of municipal solid waste incinerator (MSWI) bottom ash slag blended cements (SBC) with various replacement ratios. The 90-day compressive strengths developed by SBC pastes with 10% and 20% cement replacement by slags generated from the bottom ash were similar to that developed by ordinary Portland cement pastes. Thermal analyses indicated that the hydrates in the SBC pastes were mainly portlandite (Ca(OH)₂) and calcium silicate hydrate (C–S–H) gels, similar to those found in ordinary Portland cement paste. It is also indicated that the slag reacted with Ca(OH)₂ to form C–S–H. The average length (in terms of the number of Si molecules) of linear polysilicate anions in C–S–H gel, as determined by ²⁹Si nuclear magnetic resonance, increased in all the SBC pastes with increasing curing age, which outperformed that of ordinary Portland cement at 90 days. It can thus be concluded from the study results, that municipal solid waste incinerator bottom ash can be processed by melting to obtain reactive pozzolanic slag, which may be used in SBC to partially replace the cement.     

Logistics cost analysis of rice straw pellets for feasible production capacity and spatial scale in heat utilization systems: A case study in Nanporo town,Hokkaido, Japan

Rice straw is a promising renewable energy source because it is abundantly available in Asia. This study conducted a case study of logistics cost analysis for rice straw pellets by considering all stages in the supply chain to define the main factors affecting the selling price of rice straw pellets: collection (job-commission or employment of part-time workers), transportation, storage (vinyl greenhouses or storage buildings with larger capacity), pelletizing, and delivery to users with biomass boilers. The selling price was found to be strongly dependent on the production capacity because the investment cost for the pellet production facility had a significant effect of economies of scale. A production capacity of larger than 1500 t y⁻¹ is required for rice straw pellets to compete with wood pellets and fossil fuels in the studied Japanese context if the subsidy rate for the investment is 50%, part-time workers conduct the collection, and rice straw is stored in the storage buildings. Our sensitivity analysis also showed an economically feasible spatial scale: for example, rice straw should be collected within a 20 km radius and the users should be within a 38 km radius when the production capacity is 1500 t y⁻¹. In addition, other critical factors related to the collection of rice straw from the paddy fields and transportation of rice straw rolls to storage were identified as planning factors to further reduce the total logistics cost of rice straw pellets.     

Mixed hemimicelle solid-phase extraction based on magnetic carbon nanotubes and ionic liquids for the determination of flavonoids

A novel mixed hemimicelles solid phase extraction (SPE) based on magnetic carbon nanotubes (MCNTs) and ionic liquid (IL) is developed for the simultaneous extraction and determination of trace flavonoids in spiked human urine. In this novel SPE, the formation of C₁₆mimBr with mixed hemimicelles on the surface of MCNTs@SiO₂ nanoparticles (NPs) causes retention of analytes by strong hydrophobic, π–π and electrostatic interactions. This SPE technique combines the advantages of mixed hemimicelles and MCNTs. In order to establish the guidelines for the preparation of mixed hemimicelles on composite materials, different main factors affecting the preconcentration of analytes, such as material type, amount of surfactant, pH of solution, ionic strength, extraction time, desorption condition and regeneration property, were investigated and optimized. Under the selected conditions, the accuracy of the method was evaluated by recovery measurements on spiked samples, and good recoveries with low relative standard deviations from 3.5% to 4.9% were achieved. No interferences were caused by endogenous compounds in human urine. For our knowledge, this is the first development of a mixed hemimicelles SPE based on MCNTs and IL for the extraction of trace analytes in complex biological samples.     

Bioenergy villages in Germany: Bringing a low carbon energy supply for rural areas into practice

An increasing number of rural municipalities wants to meet their entire energy demand with biomass. This article gives a system analytic view on these “bioenergy villages” by balancing pros (reduction of CO₂ emissions) and cons (increasing costs, land use) using the example of a model municipality in Germany. The results indicate that a 100% energy supply based on biomass from within the boundaries of a rural municipality is technically possible but less reasonable with respect to land use competition and costs of energy supply. Whereas heat and power demand in bioenergy villages can be covered with relatively little land use and to relatively low costs, the production of transport fuel based on energy crops (rape seed) leads to significant negative impacts. For a cost-efficient decarbonization of rural areas it can therefore be recommended to particularly expand the utilization of biomass for heat and power production and to reconsider the transport fuel production.