Vacuum ammonia stripping from liquid digestate: Effects of pH, alkalinity, temperature, negative pressure and process optimization.

High ammonia-nitrogen digestate has become a key bottleneck limiting the anaerobic digestion of organic solid waste. Vacuum ammonia stripping can simultaneously remove and recover ammonia nitrogen, which has attracted a lot of attention in recent years. To investigate the parameter effects on the efficiency and mass transfer, five combination conditions (53 °C 15 kPa, 60 °C 20 kPa, 65 °C 25 kPa, 72 °C 35 kPa, and 81 °C 50 kPa) were conducted for ammonia stripping of sludge digestate. The results showed that 80% of ammonia nitrogen was stripped in 45 min for all experimental groups, but the ammonia transfer coefficient varied under different conditions, which increased with the rising of boiling point temperature, and reached the maximum value (39.0 mm/hr) at 81 °C 50 kPa. The ammonia nitrogen removal efficiency was more than 80% for 30 min vacuum stripping after adjusting the initial pH to above 9.5, and adjustment of the initial alkalinity also affects the pH value of liquid digestate. It was found that pH and alkalinity are the key factors influencing the ammonia nitrogen dissociation and removal efficiency, while temperature and vacuum mainly affect the ammonia nitrogen mass transfer and removal velocity. In terms of the mechanism of vacuum ammonia stripping, it underwent alkalinity destruction, pH enhancement, ammonia nitrogen dissociation, and free ammonia removal. In this study, two-stage experiments of alkalinity destruction and ammonia removal were also carried out, which showed that the two-stage configuration was beneficial for ammonia removal. It provides a theoretical basis and practical technology for the vacuum ammonia stripping from liquid digestate of organic solid waste.

The Phase Distribution Characteristics and Interphase Mass Transfer Behaviors of the CO2-Water/Saline System under Gathering and Transportation Conditions: Insights on Molecular Dynamics.

In order to investigate the interphase mass transfer and component distribution characteristics of the CO2-water system under micro-scale and nano-scale transport conditions, a micro-scale kinetic model representing interphase mass transfer in the CO2-water/saline system is developed in this paper. The molecular dynamics method is employed to delineate the diffusion and mass transfer processes of the system's components, revealing the extent of the effects of variations in temperature, pressure, and salt ion concentration on interphase mass transfer and component distribution characteristics. The interphase mass transfer process in the CO2-water system under transport conditions can be categorized into three stages: approach, adsorption, and entrance. As the system temperature rises and pressure decreases, the peak density of CO2 molecules at the gas-liquid interface markedly drops, with their aggregation reducing and their diffusion capability enhancing. The specific hydration structures between salt ions and water molecules hinder the entry of CO2 into the aqueous phase. Additionally, as the salt concentration in water increases, the density peak of CO2 molecules at the gas-liquid interface slightly increases, while the density value in the water phase region significantly decreases.

Application of a UV-vis spectrometer to investigate the effect of dissolution media on the diffusivity of small molecules and proteins.

To date, the commonly used methods for diffusion coefficient measurements have some hurdles that prevent them from being widely applied in pharmaceutical laboratories. This study aimed to modify a method developed by di Cagno et al. based on the use of a UV-Vis spectrometer and apply the method to investigate the effect of dissolution media on the diffusivity of small molecules and proteins. A total of five small molecules and two proteins in different aqueous media and polymer solutions were investigated in this study. By attaching a 3D-printed cover with an open slit to a standard UV-Vis cuvette, the incident UV light could only pass through the open slit to measure the local drug concentration. During the diffusion experiment, drug molecules diffused from the cuvette bottom to the slit. According to the concentration measured as a function of time, diffusion coefficient was calculated based on Fick's law of diffusion using the analytical and numerical approaches. As a result, diffusion coefficients could be accurately measured with high reproducibility. The results also suggested that different media could affect the diffusion coefficients of small molecules by < 10% and proteins by < 15%. Since the UV-Vis spectrometer is a routine instrument, this method can potentially be employed by many pharmaceutical laboratories for diffusion coefficient measurements.

Exploring Osmotic Dehydration for Food Preservation: Methods, Modelling, and Modern Applications.

This study summarizes the most recent findings on osmotic dehydration, a crucial step in food preservation. The many benefits of osmotic dehydration are listed, including longer shelf life and preserved nutritional value. Mass transfer dynamics, which are critical to understanding osmotic dehydration, are explored alongside mathematical models essential for comprehending this process. The effect of osmotic agents and process parameters on efficacy, such as temperature, agitation and osmotic agent concentration, is closely examined. Pre-treatment techniques are emphasized in order to improve process effectiveness and product quality. The increasing demand for sustainability is a critical factor driving research into eco-friendly osmotic agents, waste valorization, and energy-efficient methods. The review also provides practical insights into process optimization and discusses the energy consumption and viability of osmotic dehydration compared to other drying methods. Future applications and improvements are highlighted, making it an invaluable tool for the food industry.

Mass Transfer Resistance and Reaction Rate Kinetics for Carbohydrate Digestion with Cell Wall Degradation by Cellulase.

This paper introduces an enzymatic approach to estimate internal mass-transfer resistances during food digestion studies. Cellulase has been used to degrade starch cell walls (where cellulose is a significant component) and reduce the internal mass-transfer resistance, so that the starch granules are released and hydrolysed by amylase, increasing the starch hydrolysis rates, as a technique for measuring the internal mass-transfer resistance of cell walls. The estimated internal mass-transfer resistances for granular starch hydrolysis in a beaker and stirrer system for simulating the food digestion range from 2.2 × 107 m-1 s at a stirrer speed of 100 rpm to 6.6 × 107 m-1 s at 200 rpm. The reaction rate constants for cellulase-treated starch are about three to eight times as great as those for starch powder. The beaker and stirrer system provides an in vitro model to quantitatively understand external mass-transfer resistance and compare mass-transfer and reaction rate kinetics in starch hydrolysis during food digestion. Particle size analysis indicates that starch cell wall degradation reduces starch granule adhesion (compared with soaked starch samples), though the primary particle sizes are similar, and increases the interfacial surface area, reducing internal mass-transfer resistance and overall mass-transfer resistance. Dimensional analysis (such as the Damköhler numbers, Da, 0.3-0.5) from this in vitro system shows that mass-transfer rates are greater than reaction rates. At the same time, SEM (scanning electron microscopy) images of starch particles indicate significant morphology changes due to the cell wall degradation.

Understanding the role of flux chamber configuration in the measurement of VOC emissions from porous media.

The accurate quantification of volatile organic compound (VOC) emission rates from porous media to the air is a challenging problem, as measurements are affected by the chemical and physical characteristics of the porous media, and the operating parameters of the sampling device itself. The main objective of this study is to investigate how flux chamber (the most commonly used sampling device) configurations influence emission rate measurement from three selected porous media. Various parameters were studied, including sweep air flow rate, presence of a mixing fan, headspace volume and thickness of media. Controlled experiments focused on the behaviour of two VOCs commonly found in area sources: acetic acid and 1-butanol. Sweep gas flow rate emerged as the most influential factor, inducing turbulence and dilution over porous media surfaces and impacting emission rate measurements more significantly than headspace volume and fan installation. Variations in porous media properties also affected mass transfer, with emissions from coco coir showing higher mass transfer as its porosity and particle size facilitated gas transportation. While behaviour of acetic acid emission through the media supported the diffusion theory, emission of 1-butanol was affected by a combination of factors, highlighting the role of both diffusive and advective transport mechanisms. Understanding how flux chamber setups and porous media properties influence emission rates is crucial for accurately interpreting data. This knowledge also guides the design of studies, especially when investigating complex sources like biosolids and organic-amended soil.

Analysis of fractionalized Brinkman flow in the presence of diffusion effect.

A vertical plate experiences a dynamic flow of fractionalized Brinkman fluid governed by fluctuating magnetic forces. This study considers heat absorption and diffusion-thermo effects. The novelty of model is the fractionalized Fourier's and Fick's laws. The problem is solved using the constant proportional Caputo derivative and Laplace transform method. The resulting non-dimensional equations for temperature, mass, and velocity fields are solved and compared visually. We explore the influence of various parameters like the fractional order, heat absorption/generation (Q), chemical reaction rate (R), and magnetic field strength (M) through informative graphs. Additionally, we contrast the velocity fields of fractionalized and regular fluids. The visualizations reveal that diffusion-thermo and mass Grashof number enhance fluid velocity, while chemical reaction and magnetic field tend to suppress it. For the interest of engineering, physical quantities such as Sherwood number, skin friction, and Nusselt number are computed. The present study satisfying all initial and boundary condition can be reduced to to previous published work which shows the validity of present work.

Comprehensive Study on the Electrochemical Evolution, Reaction Kinetics, and Mass Transport at the Anion Exchange Ionomer-Pt Interface for Oxygen Reduction Reaction.

Understanding the structure evolution, kinetics, and mass transfer for the oxygen reduction reaction (ORR) at the ionomer-catalyst interface is fundamental for the development of anion exchange membrane fuel cells (AEMFCs). Herein, we investigate the structural evolution of ionomer-Pt interfaces during the activation process of polycrystalline Pt (poly-Pt) electrodes and their ORR kinetics and mass transfer characteristics at steady state. The results suggest the ionomer thickness as a critical factor in determining the Pt surface structure and the flux of the O2 diffusion, which in turn affect the subsequent kinetic and mass transfer of the ORR on ionomer-Pt electrode interfaces. Thicker ionomer film leads to a more severe evolution of electrochemical features during the activation process, likely caused by forming more less-active Pt clusters at the ionomer-Pt interface. Thus, the ORR kinetic activity at the steady state decreases with the increase in ionomer thickness. Concurrently, the thicker ionomer leads to a reduced diffusion flux of O2, culminating in a lower limiting current density for the ORR. Additionally, we calculated the diffusion coefficient and solubility of O2 within the FAA-3 alkaline ionomer film, with a comparative assessment against those in the proton exchange membrane (PEM). These findings offer valuable insights into the ionomer-Pt interface in AEMFCs and their effects on performance.

Analysis of the Discharge Termination Mechanism of a Nonaqueous Li-O2 Battery Based on a Digital Reconstruction Model.

The service life of the lithium-oxygen (Li-O2) battery is an essential factor in measuring the performance of the battery, and it is also imperative to clarify the reason for battery termination. In this work, the positive electrode of a nonaqueous Li-O2 battery was selected after cutoff under different discharge conditions, and the digital reconstruction model of the positive electrode was carried out by X-CT technology. The reconstructed positive electrode's structural characteristics, material transport characteristics, and electrical conductivity were analyzed. It is found that the positive electrode has an apparent expansion phenomenon after constant capacity cyclic charge and discharge, but this situation is not evident after deep discharge. After the constant capacity test is cut off, the product distribution range in the positive electrode is more comprehensive and the material transport efficiency is higher. However, after deep discharge, the product distribution in the positive electrode is more concentrated and the material transport efficiency is lower. There are apparent differences in the termination mechanism between constant capacity cycle discharge and deep discharge. This paper provides a compelling theoretical basis for revealing the discharge termination mechanism of nonaqueous Li-O2 batteries.

Moment analysis method for the determination of permeation kinetics of coumarin at lipid bilayers of liposomes by using capillary electrophoresis.

A method was developed for studying mass transfer kinetics at lipid bilayers of liposomes. Elution peaks of coumarin were measured by liposome electrokinetic chromatography (LEKC). Four types of phospholipids having different alkyl chains were used for preparing liposomes, which were used as pseudo-stationary phases in LEKC systems. Rate constants of permeation across lipid bilayers of liposomes or of adsorption at lipid membranes were determined by analyzing the first absolute and second central moments of the elution peaks measured by LEKC. The rate constants of permeation or adsorption tend to decrease with an increase in the carbon number of the alkyl chains of phospholipids. It was demonstrated that the moment analysis of elution peak profiles measured by LEKC is effective for determining lipid membrane permeability or adsorption kinetics. Compared with other conventional techniques, the method has some advantages for studying mass transfer kinetics at lipid bilayers. Solute permeation across or solute adsorption at real lipid bilayers of liposomes is analyzed. The principle of the method is the analysis of separation behavior in LEKC, which is different from that of the other ones. It is expected that the method contributes to the kinetic study of mass transfer at lipid bilayers from various perspectives.

Mass transfer in heterogeneous biofilms: Key issues in biofilm reactors and AI-driven performance prediction.

Biofilm reactors, known for utilizing biofilm formation for cell immobilization, offer enhanced biomass concentration and operational stability over traditional planktonic systems. However, the dense nature of biofilms poses challenges for substrate accessibility to cells and the efficient release of products, making mass transfer efficiency a critical issue in these systems. Recent advancements have unveiled the intricate, heterogeneous architecture of biofilms, contradicting the earlier view of them as uniform, porous structures with consistent mass transfer properties. In this review, we explore six biofilm reactor configurations and their potential combinations, emphasizing how the spatial arrangement of biofilms within reactors influences mass transfer efficiency and overall reactor performance. Furthermore, we discuss how to apply artificial intelligence in processing biofilm measurement data and predicting reactor performance. This review highlights the role of biofilm reactors in environmental and energy sectors, paving the way for future innovations in biofilm-based technologies and their broader applications.

The influence of geographical location on moisture distribution in wood cross sections: a numerical simulation study using Austria as an example.

Wood constantly interacts with the surrounding, locally varying climate, leading to changes in the moisture content. Advanced simulation tools can predict the two-dimensional moisture distributions caused by these changing climate conditions within wood cross sections over time. However, there is a notable absence of systematic simulation results for diverse climatic conditions and various wood cross sections. This study seeks to bridge this gap in research. Here, we present moisture fields in three solid timber and three glued laminated timber cross sections in Austria and show the effect of the location and the altitude on the moisture content distribution. The results reveal decreasing influence of the location on the moisture content development with increasing cross section size, and primarily the altitude affecting the moisture content. In addition, the results are compared with the standard for the design of timber-concrete composite structures (ONR CEN/TS 19103), revealing appropriate values in most of the cases. Only for cross sections with a width of 14 cm and larger, assigned to a specific region, the standard value is assumed underestimated. Furthermore, the distribution of moisture gradients, which are related to the crack depth development, are analyzed for Austria, demonstrating the influence of mountain areas in the moisture gradient development. Supplementary Information: The online version contains supplementary material available at 10.1186/s10086-024-02147-z.

Study on quality characteristics, shelf-life prediction and frying mass transfer of breaded tilapia nuggets.

Deep-fried breaded tilapia nuggets (DFBTNs) have good market prospects as a tilapia deep-processed product. In this study, we used pre-optimized DFBTNs to simulate the mass change from storage to consumption and investigated the changes in storage shelf-life and frying mass transfer kinetics of DFBTNs. Microbial growth trend and shelf-life prediction models at different storage temperatures were developed using a modified Gompertz equation. The R2 of the fitted equations were all greater than 0.98, and the predicted shelf-life of the products was close to the actual measurement time. The ability of the electronic nose and tongue to differentiate between odor and taste can be used as a secondary indicator to determine whether a product is spoiled or not. During the reheating process of deep-frying, the batter shell moisture decreased (18.69 %→6.89 %), and the oil content increased (2.76 %→27.35 %). The mass transfer coefficient k fitted by Fick's second law for moisture evaporation was 0.0086, and the mass transfer coefficient k fitted by the first-order kinetic equation for oil absorption was 0.1137. This study is informative for storing and consuming DFBTNs, which can provide a basis for the deep processing and high-value utilization of tilapia.

[Mass transfer of bilirubin and bovine serum albumin in hollow fiber membrane module of artificial liver].

Understanding the mass transfer behaviors in hollow fiber membrane module of artificial liver is important for improving toxin removal efficiency. A three-dimensional numerical model was established to study the mass transfer of small molecule bilirubin and macromolecule bovine serum albumin (BSA) in the hollow fiber membrane module. Effects of tube-side flow rate, shell-side flow rate, and hollow fiber length on the mass transfer of bilirubin and BSA were discussed. The simulation results showed that the clearance of bilirubin was significantly affected by both convective and diffusive solute transport, while the clearance of macromolecule BSA was dominated by convective solute transport. The clearance rates of bilirubin and BSA increasd with the increase of tube-side flow rate and hollow fiber length. With the increase of shell-side flow rate, the clearance rate of bilirubin first rose rapidly, then slowly rose to an asymptotic value, while the clearance rate of BSA gradually decreased. The results can provide help for designing structures of hollow fiber membrane module and operation parameters of clinical treatment.

Oxygen reduction reaction coupled electro-oxidation for highly-efficient and sustainable water treatment.

Electro-oxidation (EO) technology demonstrates significant potential in wastewater treatment. However, the high energy consumption has become a pivotal constraint hindering its large-scale implementation. Herein, we design an EO and 4-electron oxygen reduction reaction coupled system (EO-4eORR) to replace the traditional EO and hydrogen evolution reaction (HER) coupled system (EO-HER). The theoretical cathodic potential of the electrolytic reactor is tuned from 0 V (vs. RHE) in HER to 1.23 V (vs. RHE) in 4eORR, which greatly decreases the required operation voltage of the reactor. Moreover, we demonstrate that convection can improve the mass transfer of oxygen and organic pollutants in the reaction system, leading to low cathodic polarization and high pollutant removal rate. Compared with traditional EO-HER system, the energy consumption of the EO-4eORR system under air aeration for 95% total organic carbon (TOC) removal is greatly decreased to 2.61 kWh/kgTOC (only consider the electrolyzer energy consumption), which is superior to previously reported EO-based water treatment systems. The reported results in this study offer a new technical mode for development of highly efficient and sustainable EO-based treatment systems to remove organic pollutants in waste water.

3D Bioprinting of Engineered Living Materials with Extracellular Electron Transfer Capability for Water Purification.

Attention is widely drawn to the extracellular electron transfer (EET) process of electroactive bacteria (EAB) for water purification, but its efficacy is often hindered in complex environmental matrices. In this study, the engineered living materials with EET capability (e-ELMs) were for the first time created with customized geometric configurations for pollutant removal using three-dimensional (3D) bioprinting platform. By combining EAB and tailored viscoelastic matrix, a biocompatible and tunable electroactive bioink for 3D bioprinting was initially developed with tuned rheological properties, enabling meticulous manipulation of microbial spatial arrangement and density. e-ELMs with different spatial microstructures were then designed and constructed by adjusting the filament diameter and orientation during the 3D printing process. Simulations of diffusion and fluid dynamics collectively showcase internal mass transfer rates and EET efficiency of e-ELMs with different spatial microstructures, contributing to the outstanding decontamination performances. Our research propels 3D bioprinting technology into the environmental realm, enabling the creation of intricately designed e-ELMs and providing promising routes to address the emerging water pollution concerns.

Progress on hydrogen sulfide removal: From catalytic oxidation to plasma-assisted treatment.

Air pollution is a long-standing environmental challenge as well an important economic subject. Hydrogen sulfide is one the major pollutants in the industrial releases. This review focuses on the thermochemical treatment of hydrogen sulfide based on the most recent works to date regarding its removal. By analyzing fundamental steps in chemical reaction engineering, some useful factors are emphasized since they are often neglected in scientific studies, catalysts design and process scale-up. From processing side, the fluid flow conditions including velocity, H2S concentration, relative humidity, temperature and pressure strongly influence the kinetic behavior and so the catalytic performance of the H2S removal reactor. From material side, the catalyst properties including nature, porosity, pore types, size, sites distribution and layer structuration largely influence the removal performance via among others the accessibility to catalytic sites, pores connection and mass transfer resistance. Plasma-assisted catalytic removal of H2S combines many novelties in comparison with a classical thermo-catalytic process. From patents review, we can see that main concerns are about electrodes mounting, reactor lifetime and modular design to solve the problems in the industrial practice. We attempt to provide for scientists, engineers and industrialists a guidance on the design of catalysts and processes for H2S removal which could be applied in laboratorial studies and industrial processes as well.

Sustainable protein/polysaccharide aerogel for the simultaneous and efficient removal of multiple organic contaminants: Insights from DFT calculations and phenomenological mass-transfer modeling.

Wastewater contains various organic contaminants that pose great hazards to human health and the environment. A protein/polysaccharide-derived aerogel, namely, ICMA, was developed as a high-performance adsorbent for the simultaneous and efficient removal of diverse contaminants from wastewater, including melanoidin (MLE), Congo red (CR), and diclofenac (DIC). Metal organic framework (UiO-66-NH2), as a regulatory factor, significantly improved the porosity and pore volume of the ICMA to enhance the capture performance of contaminants. The ICMA exhibited outstanding adsorption efficiency owing to the incorporation of ample polyamine functional groups and its well-developed pore structure, large porosity and pore volume, and remarkable heat resistance. The equilibrium capture capacities of the ICMA were 1364, 2031, and 539 mg/g for MLE, CR, and DIC, respectively, with corresponding removal efficiencies all exceeding 90%. Furthermore, the ICMA can capture cationic dyes through MLE/CR/DIC-bridging interactions. After five cycles, the used ICMA can still maintain a high contaminant removal rate/amount, demonstrating good reusability. The classic adsorption model showed that the capture of contaminants by the ICMA is a double-layered and heterogeneous adsorption orientation. A brand new LWAMTM model demonstrated that the adsorption mass-transfer process is jointly determined by the external mass conveyance, pore diffusion, and adsorption on the active site. Multiple characterizations indicated that the contaminant adsorption onto the ICMA was mainly facilitated by charge interactions, with H-bonds playing a secondary role. Quantum chemical theory simulations further provide insights into the atomic-level mechanisms involved in the capture of contaminants. Hirshfeld surface analysis revealed that the ICMA functions as both an H-bond acceptor and a donor during contaminant adsorption. Scale-up and upgrade adsorption were performed to treat actual/simulated wastewater, establishing the groundwork for the industrial implementation of the ICMA.

A Nanoconfined FeCo2O4-Embedded Ceramic Membrane Regulates Electron Transfer in Peroxymonosulfate Activation to Selectively Generate Singlet Oxygen for Water Decontamination.

Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs), as a promising technology for water decontamination, are constrained by low reaction kinetics due to limited reaction selectivity and mass transfer. Herein, we designed a nanoconfined FeCo2O4-embedded ceramic membrane (FeCo2O4-CM) under flow-through pattern for PMS activation. Confining PMS and FeCo2O4 within nanochannels (3.0-4.7 nm) enhanced adsorption interactions (-7.84 eV vs -2.20 eV), thus boosting mass transfer. Nanoconfinement effect regulated electron transfer pathways from PMS to FeCo2O4-CM by modulating the active site transformation to ≡Co(III) in nanoconfined FeCo2O4-CM, enabling selectively generating 1O2. The primary role of 1O2 in the nanoconfined system was confirmed by kinetic solvent isotope experiments and indicative anthracene endoperoxide (DPAO2). The system enabled 100% removal of atrazine (ATZ) within a hydraulic retention time of 2.124 ms, demonstrating a rate constant over 5 orders of magnitude higher than the nonconfined system (3.50 × 103 s-1 vs 0.42 min-1). It also exhibited strong resilience to pH variations (3.3-9.0) and coexisting substances, demonstrating excellent stability indicated by consistent 100% ATZ removal for 14 days. This study sheds light on regulating electron transfer pathways to selectively generate 1O2 through the nanoconfinement effect, boosting the practical application of PMS-based AOPs in environmental remediation and potentially applying them to various other AOPs.

Heat transfer processes in 'Shine Muscat' grapevine leaves in solar greenhouses under different irrigation treatments.

The use of solar greenhouses in China is increasing because they permit environmental conditions to be controlled. Studies of the heat transfer processes in the leaves of plants cultivated within solar greenhouses are needed. Here, we studied heat transfer processes in 'Shine Muscat' grapevine leaves under moderate deficit irrigation (MDI), severe deficit irrigation (SDI), and full irrigation (FI) treatments under varying weather conditions. The stomatal conductance, leaf temperature, and transpiration rate of both shade and sun grapevine leaves were measured, and the effects of ambient temperature and relative humidity on these variables were determined. A thermal physics model of the leaves was established to explore the heat dissipation process. On sunny days, the transpiration heat transfer of sun leaves in the MDI, SDI, and FI treatments was 2.62 MJ m-2·day-1, 2.44 MJ m-2·day-1, and 3.86 MJ m-2·day-1and 0.818 MJ m-2·day-1, 0.782 MJ m-2·day-1, and 1.185 MJ m-2·day-1 on rainy days, respectively. There was a significant difference in transpiration heat transfer under fully irrigated and deficit irrigation conditions under different weather conditions. Furthermore, transpiration heat transfer accounted for 41.49 % and 25.03 % of the total heat transfer of sun leaves in the FI treatment and 33.94 % and 29.43 % of the total heat transfer of shade leaves on rainy days, respectively, indicating that relative humidity plays a key role in determining transpiration heat transfer and leaf temperature and that its effect was greater on sun leaves than on shade leaves.