Mechanisms of the Higher Catalytic Activity of Polymer Forms over Complexes for Non-pyrolytic Mono-1,10-phenanthroline-Coordinated Cu2+ (Cu-N2 Type) in an Oxygen Reduction Reaction.

In this paper, we have thoroughly investigated the ORR mechanism of non-pyrolytic mono-1,10-phenanthroline-coordinated Cu2+ (Cu-N2 type) complexes and polymers by molecular dynamics and quantum mechanics calculation. In contrast to the complex-catalyzed ORR, which follows a direct four-electron pathway along intermediates of Cu(I)-Phen, the polymer-catalyzed ORR follows an indirect four-electron pathway by intermediates of Cu(II)-Phen. By analyzing the structure, spin population, electrostatic potential (ESP), and density of states, we confirmed that the higher ORR catalytic activity of the polymer is due to the conjugation effect of coplanar phenanthroline and Cu(II) in the planar reactants or at the base of the square-pyramidal intermediates. The conjugation effect allows the highest ESP to be located near the active center Cu(II), while the lower ESPs are distributed on the phenanthroline, which is very favorable for the reduction current. This will serve as a theoretical foundation for the development of new highly efficient ORR non-pyrolytic CuN2 polymer catalysts.

Quantitative relationship between the structures and properties of VOCs and SOA formation on the surfaces of acidic aerosol particles.

In this research, all the efforts, based on a series of molecular dynamics simulations on the interfacial process between VOC-contaminated air and acidic sulfate, were made to find how the structures and properties of VOCs are related to the formation of SOAs. The experimental fractional aerosol coefficients (FACs) were used to quantify the SOA formation and 14 VOC species were chosen based on the atmosphere inventory and the FAC magnitude. Finally, the quantitative relationship (QR) was found through the FAC as a function of the two variables the total valid interactions (Tg) and the diffusion coefficient (D), with R square 0.94. Meanwhile, the effect of water was explored and the QR was proved to be rational and reliable. The QR not only explained the SOA formation capacity of VOCs, but could also predict the SOA formation of new molecules.

Visualizing the macroscale spatial distributions of biofilms in complex flow channels using industrial computed tomography.

The presence of biofilms in enclosed pipelines can lead to numerous deleterious issues. To date, it has been difficult to use optical imaging techniques to monitor the macroscale spatial distributions of biofilms. To address this concern, a combination of industrial computed tomography (ICT) and a contrast agent was explored to noninvasively visualize biofilms in three types of drip irrigation emitters. The results showed that ICT successfully observed and quantified the macroscale spatial distributions of biofilms. The complex hydrodynamic characteristics in the emitter channels affected the local distributions of biofilms. Biofilms were mainly attached to the lateral and medial faces and biomass decreased along the flow directions. Based on the distributions of biofilms, some emitter structural design defects were further diagnosed. Applying ICT in combination with the contrast agent could potentially provide a visual and effective way to reveal the formation mechanisms of biofilms and to optimize flow channel structures to avoid biofilm accumulations.

Jungle on the Electrode: A Target-Induced Enzyme-Free and Label-Free Biosensor.

With the development of clinical medicine-related technologies, the detection of cancer biomarkers has become an essential method for cancer diagnosis. DNA self-assembly is a valuable approach to monitor low-abundance miRNA. Herein, we report a novel DNA jungle biosensor for target-induced enzyme-free and label-free ultrasensitive detection of miRNA-21 in biological samples. The method consists of two parts. The target catalyzes the assembly of the hairpin to form the backbone of the DNA jungle, and the auxiliary probes hybridize to form branches freely and undirectedly. The DNA jungle can be self-assembled seeded from a single target initiator, affording the potential for screening a single target molecule. Vitro assays show that the DNA jungle offers very high amplification efficiency and specificity, with a direct detection limit of 1 aM. This DNA jungle strategy can provide a useful platform for low-abundance biomarker detection for cell biology and diagnostics.

The influence of chlorination timing and concentration on microbial communities in labyrinth channels: implications for biofilm removal.

Chlorination is an effective method to control biofilm formation in enclosed pipelines. To date, very little is known about how to control biofilms at the mesoscale in complex pipelines through chlorination. In this study, the dynamic of microbial communities was examined under different residual chlorine concentrations on the biofilms attached to labyrinth channels for drip irrigation using reclaimed water. The results indicated that the microbial phospholipid fatty acids, extracellular polymeric substances, microbial dynamics, and the ace and Shannon microbial diversity indices showed a gradual decrease after chlorination. However, chlorination increased microbial activity by 0.5-19.2%. The increase in the relative abundances of chloride-resistant bacteria (Acinetobacter and Thermomonas) could lead to a potential risk of chlorine resistance. Thus, keeping a low chlorine concentration (0.83 mg l-1 for 3 h) is effective for controlling biofilm formation in the labyrinth channels.

Green infrastructure practices simulation of the impacts of land use on surface runoff: Case study in Ecorse River watershed, Michigan.

As an urban fringe district, the Ecorse River watershed is faced with increased impervious area caused by urban expansion. Effects of Green Infrastructure (GI) practice implementation were simulated with the Long-Term Hydrologic Impact Assessment-Low Impact Development 2.1 model (L-THIA-LID 2.1). Suitable locations of each GI practice were identified, based on construction condition requirements and demand on GI practices in the study area. Using the data of 2011, various GI practice combination scenarios were explored according to the cost-efficiency of each GI practice. GI practice implementation scenarios in 2050 were also simulated based on projected land use and rainfall data. Results show that grassed swales, rain barrels (residential areas) and dry ponds were the top three most cost-efficient GI practices, with the cost at $1.5/m³/yr, $3.0/m³/yr and $3.4/m³/yr, respectively. Green roofs with rain cisterns (industrial and commercial area) were the most expensive GI practices, with the cost at $92.9/m³/yr. With the increase of investment in GI practices, the changing curves of the annual runoff volume, Total Nitrogen (TN) load and Total Phosphorus (TP) load reduction ratios match the law of diminishing marginal utility. The scenario with grassed swales, rain barrels, dry ponds and porous pavement would be the most cost-efficient scenario for runoff water quantity reduction. In addition, the scenario with additional wet ponds would be the most cost-efficient one for TN load and TP load reduction. GI practices in each scenario for expected 2050 conditions show better effectiveness on water quantity and quality management.

Single Layer Surface-Grafted PMMA as a Negative-Tone e-Beam Resist.

One of the important challenges in electron beam lithography is nanofabrication on nonflat or irregular surfaces. Although spin coating is the most popular technique for resist coating, it is not suitable for nonflat, irregular substrates because a uniform film cannot be achieved on those surfaces. Here, it is demonstrated that single layer surface-grafted PMMA can be used as a negative-tone e-beam resist, and it can be applied to nonflat, irregular surfaces as well as flat, conventional surfaces. Although it is well known that heavily exposed PMMA undergoes cross-linking and works as a negative-tone e-beam resist when developed by solvent, solvent does not work as a developer for negative-tone single-layer surface-grafted PMMA. Instead, thermal treatment at 360 °C for 1 min is used to develop PMMA.

Retrofitting LID Practices into Existing Neighborhoods: Is It Worth It?

Low-impact development (LID) practices are gaining popularity as an approach to manage stormwater close to the source. LID practices reduce infrastructure requirements and help maintain hydrologic processes similar to predevelopment conditions. Studies have shown LID practices to be effective in reducing runoff and improving water quality. However, little has been done to aid decision makers in selecting the most effective practices for their needs and budgets. The long-term hydrologic impact assessment LID model was applied to four neighborhoods in Lafayette, Indiana using readily available data sources to compare LID practices by analyzing runoff volumes, implementation cost, and the approximate period needed to achieve payback on the investment. Depending on the LID practice and adoption level, 10-70% reductions in runoff volumes could be achieved. The cost per cubic meter of runoff reduction was highly variable depending on the LID practice and the land use to which it was applied, ranging from around $3 to almost $600. In some cases the savings from reduced runoff volumes paid back the LID practice cost with interest in less than 3 years, while in other cases it was not possible to generate a payback. Decision makers need this information to establish realistic goals and make informed decisions regarding LID practices before moving into detailed designs, thereby saving time and resources.

Enhancing a rainfall-runoff model to assess the impacts of BMPs and LID practices on storm runoff.

Best management practices (BMPs) and low impact development (LID) practices are increasingly being used as stormwater management techniques to reduce the impacts of urban development on hydrology and water quality. To assist planners and decision-makers at various stages of development projects (planning, implementation, and evaluation), user-friendly tools are needed to assess the effectiveness of BMPs and LID practices. This study describes a simple tool, the Long-Term Hydrologic Impact Assessment-LID (L-THIA-LID), which is enhanced with additional BMPs and LID practices, improved approaches to estimate hydrology and water quality, and representation of practices in series (meaning combined implementation). The tool was used to evaluate the performance of BMPs and LID practices individually and in series with 30 years of daily rainfall data in four types of idealized land use units and watersheds (low density residential, high density residential, industrial, and commercial). Simulation results were compared with the results of other published studies. The simulated results showed that reductions in runoff volume and pollutant loads after implementing BMPs and LID practices, both individually and in series, were comparable with the observed impacts of these practices. The L-THIA-LID 2.0 model is capable of assisting decision makers in evaluating environmental impacts of BMPs and LID practices, thereby improving the effectiveness of stormwater management decisions.

Physical and virtual nutrient flows in global telecoupled agricultural trade networks.

Global agricultural trade creates multiple telecoupled flows of nitrogen (N) and phosphorus (P). The flows of physical and virtual nutrients along with trade have discrepant effects on natural resources in different countries. However, existing literature has not quantified or analyzed such effects yet. Here we quantified the physical and virtual N and P flows embedded in the global agricultural trade networks from 1997 to 2016 and elaborated components of the telecoupling framework. The N and P flows both increased continuously and more than 25% of global consumption of nutrients in agricultural products were related to physical nutrient flows, while virtual nutrient flows were equivalent to one-third of the nutrients inputs into global agricultural system. These flows have positive telecoupling effects on saving N and P resources at the global scale. Reducing inefficient trade flows will enhance resource conservation, environmental sustainability in the hyper-globalized world.

Modeling and assessing water and nutrient balances in a tile-drained agricultural watershed in the U.S. Corn Belt.

Identifying the key processes and primary sources of water and nutrient losses is essential for water quantity and quality management in watersheds. This is especially true in the U.S. Corn Belt, which has been recognized as the primary region contributing nutrient loads to the Great Lakes and the Gulf of Mexico. A SWAT (Soil and Water Assessment Tool) model simulation was set up in an agricultural watershed with about 50% tile drainage area in the U.S. Corn Belt to study the water and nutrient balance components for the whole watershed and the corn-soybean rotation system. The SWAT model was improved to consider additional nitrogen and phosphorus loss paths from the soil. The model was comprehensively calibrated and validated for simulating monthly stream flow, total suspended solids (TSS), nutrient loads (including total Kjeldahl nitrogen (TKN), nitrate and nitrite nitrogen (NOx-N), total phosphorus (TP) and orthophosphate phosphorus (orthoP)), actual evapotranspiration (ETa), leaf area index (LAI) and annual crop yields in the watershed from 2011 to 2019. Results showed the model performance was very good for simulating the stream flow, TSS and ETa, and acceptable for nutrient loads, LAI and crop yields. ETa, surface runoff, lateral soil flow, tile drainage and percolation respectively accounted for 65%, 15%, 2%, 8% and 9% of the precipitation. Fertilizer was the main source of nitrogen and phosphorus input to the watershed, and harvested crops were the main paths removing nutrients. Surface runoff, tile drainage and percolation each contributed about 30% of total nitrogen losses to water, with surface runoff being dominated by organic nitrogen while tile drainage and percolation were dominated by nitrate nitrogen. Phosphorus losses were mainly through surface runoff, which resulted in 66% of the total losses and was dominated by organic phosphorus and soluble phosphorus. Representing about 49% of the watershed area, the corn-soybean rotation system contributed 83% and 88% of the total nitrogen and phosphorus inputs, respectively, to the watershed, as well as 64% and 46% of the nitrogen and phosphorus losses to the water system, respectively. The non-growing season (October to the next April) was identified as the critical period resulting in water and nutrient losses due to low evapotranspiration and plant uptake. Targeted management strategies for reducing nutrient loads in key hydrological paths were suggested.

Improvement of simulating sub-daily hydrological impacts of rainwater harvesting for landscape irrigation with rain barrels/cisterns in the SWAT model.

Rain barrels/cisterns, a popular type of low impact development (LID) practice, can restore urban hydrological processes and decrease municipal water use by harvesting roof runoff for later use, such as landscape irrigation. However, tools to assist decision makers in creating efficient rainwater harvesting and reuse strategies are limited. This study improved the Soil and Water Assessment Tool (SWAT) in simulating the subdaily hydrological impacts of rainwater harvesting for landscape irrigation with rain barrels/cisterns, including the simulation of rainwater harvesting with rain barrels/cisterns, rainwater reuse for auto landscape irrigation, evapotranspiration, initial abstraction, impervious area, soil profile, and lawn management operation. The improved SWAT was applied in the urbanized Brentwood watershed (Austin, TX) to evaluate its applicability and investigate the impacts of rainwater harvesting and reuse strategies on the reductions and reduction efficiencies (reductions per volume of rain barrels/cisterns implemented) of field scale runoff (peak and depth) and watershed scale streamflow (peak and volume) for two storm events. Scenarios explored included different sizes of rain barrels/cisterns, percentages of rooftop areas with rain barrels/cisterns implemented, auto landscape irrigation rates, and landscape irrigation starting times. The performance of rainwater harvesting and reuse strategies, which is determined by features of fields, watersheds, and storm events, varied for different reduction goals (streamflow or runoff, and peak or depth/volume). For instance, the scenario with rain barrel/cistern sizes of 7.5 mm (design runoff depth from treated roof area) and the scenario with 10% of suitable area implemented with rain barrels/cisterns provided the highest peak streamflow reduction efficiency and total streamflow volume reduction efficiency at the watershed scale, respectively for the smaller storm event. To achieve sustainable urban stormwater management, the improved SWAT model has enhanced capability to help stakeholders create efficient rainwater harvesting and reuse strategies to reduce field scale runoff and watershed scale streamflow.

Comprehensive analysis of important parameters of choline chloride-based deep eutectic solvent pretreatment of lignocellulosic biomass.

Choline chloride based deep eutectic solvents have showed great potential in lignocellulosic biomass pretreatment. In this study, for DES pretreatment with different hydrogen bond donners of different raw materials under different reaction conditions, multivariate analysis methods including principal component analysis and partial least squares analysis were used for reveal the pretreatment mechanism by evaluating the inner relationships among 42 key process factors. Furthermore, based on molecular simulation, the detailed relationships between key variables were further analyzed. Meanwhile, four-dimensional color graphs were used to intuitively reveal the synergistic influence of multivariate conditions variables on pretreatment effect to obtain better economic benefits and energy consumption indicators for DES pretreatment. The results showed that HBD hydrophilic ability, HBD polarity, HBD acidity, HBD ability to form hydrogen bonds, molar ratio of HBD to choline chloride and pretreatment severity had great influence on the Choline chloride based deep eutectic solvents pretreatment effect.

Using electromagnetic fields to inhibit biofouling and scaling in biogas slurry drip irrigation emitters.

Reusing biogas slurry (BS) in agricultural drip irrigation systems may provide a solution to deal with the adverse environmental impacts of applying BS. Biofouling and scaling are two leading issues in drip irrigation emitters. This study investigated a practice that applied electromagnetic fields (EMFs) to control biofilms and scales. The bacterial communities and mineral precipitations in the clogging substances of emitters were determined. Results showed that EMFs inhibited the growth of microbes, and influenced BS physicochemical parameters. Consequently, EMFs shifted the bacterial communities with reduced diversities. Network analyses revealed that bacterial species under EMFs treatments showed lower average connectivities and simpler interactions, which were responsible for the decreases of extracellular polymers substances (EPS). Moreover, EMFs treatments not only reduced the carbonates in emitters, but also prevented the depositions of phosphates, silicates, and quartzes. EMFs also had impacts on the lattice parameters and crystal volumes of carbonates. In addition, the changes in bacterial communities and EPS contents were associated with the reductions of various minerals. Accordingly, EMFs effectively mitigated biofilms and scales with the fixed clogging substances reduced by 29.1-53.8 %. These findings demonstrated that applying EMFs is an effective anti-biofouling and anti-scaling treatment with potential applications in BS irrigation systems.

Key process parameters for deep eutectic solvents pretreatment of lignocellulosic biomass materials: A review.

Deep eutectic solvent (DES) has been considered as a novel green solvent for lignocellulosic biomass pretreatment. The efficiency of DES pretreatment is affected by the synergy of various process parameters. The study of effect of DES physicochemical properties and pretreatment reaction conditions on the mechanism of lignocellulose biomass fractionation was of great significance for the development of biomass conversion. Form the view of process control, this review summarized recent advances in DES pretreatment, analyzed the challenges, and prospected the future development of this research field.

Evaluation of the effectiveness of green infrastructure on hydrology and water quality in a combined sewer overflow community.

Evaluation of the effectiveness of green infrastructure (GI) practices on improving site hydrology and water quality and their associated cost could provide valuable information for decision makers when creating development/re-development strategies. In this study, a watershed scale rainfall-runoff model (the Long-Term Hydrologic Impact Analysis - Low Impact Development model, the L-THIA-LID 2.1 model) was enhanced to improve its simulation of urban water management practices including GI practices. The enhanced model (L-THIA-LID 2.2) is capable of: simulating in more detail impervious surfaces including sidewalks, roads, driveways, and parking lots; conducting cost calculations for converting these impervious surfaces to porous pavements; and, selecting suitable areas for bioretention in the study area. The effectiveness of GI practices on improving hydrology and water quality in a combined sewer overflow urban watershed-the Darst Sewershed in the City of Peoria, IL-was examined in eleven simulation scenarios using 8 practices. The total cost and the cost effectiveness for each scenario considering a 20-year practice lifetime were calculated. Results showed: combined implementation of GI practices performed better than applying individual practices alone; adoption levels and combinations of GI practices could potentially reduce runoff volume by 0.2-23.5%, TSS by 0.18-30.8%, TN by 0.2-27.9%, and TP by 0.2 to 28.1%; adding more practices did not necessarily achieve substantial runoff and pollutant reductions based on site characteristics; the most cost-effective scenario out of eleven considered had an associated cost of $9.21 to achieve 1 m3 runoff reduction per year and $119 to achieve 1 kg TSS reduction per year assuming residents' cooperation in implementing GI practices on their properties; adoption of GI practices on all possible areas could potentially achieve the greatest runoff and pollutant reduction, but would not be the most cost-effective option. This enhanced model can be applied to different locations to support assessing the beneficial uses of GI practices.

A SWAT-based optimization tool for obtaining cost-effective strategies for agricultural conservation practice implementation at watershed scales.

To address the harmful algal blooms problem in Lake Erie, one solution is to determine the most cost-effective strategies for implementing agricultural best management practices (BMPs) in the Maumee River watershed. An optimization tool, which combines multi-objective optimization algorithms, SWAT (Soil and Water Assessment Tool), and a computational efficient framework, was created to optimally identify agricultural BMPs at watershed scales. The optimization tool was demonstrated in the Matson Ditch watershed, an agricultural watershed in the Maumee River basin considering critical areas (25% of the watershed with the greatest pollutant loadings per area) and the entire watershed. The initial implementation of BMPs with low expenditures greatly reduced pollutant loadings; beyond certain levels of pollutant reductions, additional expenditures resulted in less significant reductions in pollutant loadings. Compared to optimization for the entire watershed, optimization in critical areas can greatly reduce computational time and obtain similar optimization results for initial reductions in pollutant loadings, which were 10% for Dissolved Reactive Phosphorus (DRP) and 38% for Total Phosphorus (TP); however, for greater reductions in pollutant loadings, critical area optimization was less cost-effective. With the target of simultaneously reducing March-July DRP/TP losses by 40%, the optimized scenario that reduced DRP losses by 40% was found to reduce 51.1% of TP; however, the optimized scenario that reduced TP losses by 40% can only decrease 11.3% of DRP. The optimization tool can help stakeholders identify optimal types, quantities, and spatial locations of BMPs that can maximize reductions in pollutant loadings with the lowest BMP costs.

Marginal-cost-based greedy strategy (MCGS): Fast and reliable optimization of low impact development (LID) layout.

Cost effectiveness is a major concern when implementing low impact development (LID) practices for urban stormwater management (USWM). To optimize LID layout, an efficient and more reliable method, namely, the Marginal-Cost-based Greedy Strategy (MCGS) was developed based on the economic law of increasing marginal costs (MCs) and the stepwise minimization of MCs. To verify its broad applicability, MCGS was applied in three case studies in China with different system settings and environmental goals. Both Cases I and II were watershed-scale studies in Suzhou City urban districts, but in Case II, the impact of future uncertainties (i.e., climate change, urban expansion, and LID performance degradation) on USWM system performance was considered. Case III was a block-scale study of the Xixian New District (a pilot "Sponge City" in China), which involved a rainwater pipe network and a complicated environmental goal. Compared with the extensively used but complicated NSGA-II, the MCGS performed better in terms of yielding more converged performance trade-offs, providing more choices for city planners, and requiring much less computational resources in all three cases. Meanwhile, MCGS established an optimal pathway for multi-stage LID layout planning. The success of MCGS indicated that the MC of a LID practice determined its favorability in an USWM system.

Optimal implementation of green infrastructure practices to minimize influences of land use change and climate change on hydrology and water quality: Case study in Spy Run Creek watershed, Indiana.

Nutrient loading from the Maumee River watershed is a significant reason for the harmful algal blooms (HABs) problem in Lake Erie. The nutrient loading from urban areas needs to be reduced with the installation of green infrastructure (GI) practices. The Long-Term Hydrologic Impact Assessment-Low Impact Development 2.1 (L-THIA-LID 2.1) model was used to explore the influences of land use (LU) and climate change on water quantity and quality in Spy Run Creek watershed (SRCW) (part of Maumee River watershed), decide whether and where excess phosphorus loading existed, identify critical areas to understand where the greatest amount of runoff/pollutants originated, and optimally implement GI practices to obtain maximum environmental benefits with the lowest costs. Both LU/climate changes increased runoff/pollutants generated from the watershed. Areas with the highest runoff/pollutant amount per area, or critical areas, differed for various environmental concerns, land uses (LUs), and climates. Compared to optimization considering all areas, optimization conducted only in critical areas can provide similar cost-effective results with decreased computational time for low levels of runoff/pollutant reductions, but critical area optimization results were not as cost-effective for higher levels of runoff/pollutant reductions. Runoff/pollutants for 2011/2050 LUs/climates could be reduced to amounts of 2001 LU/climate by installation of GI practices with annual expenditures of $0.34 to $2.05 million. The optimization scenarios that were able to obtain the 2001 runoff level in 2011/2050, can also reduce all pollutants to 2001 levels in this watershed.

A review on effectiveness of best management practices in improving hydrology and water quality: Needs and opportunities.

Best management practices (BMPs) have been widely used to address hydrology and water quality issues in both agricultural and urban areas. Increasing numbers of BMPs have been studied in research projects and implemented in watershed management projects, but a gap remains in quantifying their effectiveness through time. In this paper, we review the current knowledge about BMP efficiencies, which indicates that most empirical studies have focused on short-term efficiencies, while few have explored long-term efficiencies. Most simulation efforts that consider BMPs assume constant performance irrespective of ages of the practices, generally based on anticipated maintenance activities or the expected performance over the life of the BMP(s). However, efficiencies of BMPs likely change over time irrespective of maintenance due to factors such as degradation of structures and accumulation of pollutants. Generally, the impacts of BMPs implemented in water quality protection programs at watershed levels have not been as rapid or large as expected, possibly due to overly high expectations for practice long-term efficiency, with BMPs even being sources of pollutants under some conditions and during some time periods. The review of available datasets reveals that current data are limited regarding both short-term and long-term BMP efficiency. Based on this review, this paper provides suggestions regarding needs and opportunities. Existing practice efficiency data need to be compiled. New data on BMP efficiencies that consider important factors, such as maintenance activities, also need to be collected. Then, the existing and new data need to be analyzed. Further research is needed to create a framework, as well as modeling approaches built on the framework, to simulate changes in BMP efficiencies with time. The research community needs to work together in addressing these needs and opportunities, which will assist decision makers in formulating better decisions regarding BMP implementation in watershed management projects.