Electrospun and functionalized PVDF/PAN nanocatalyst-loaded composite for dechlorination and photodegradation of pesticides in contaminated water

A novel approach for the electrospinning and functionalization of nanocatalyst-loaded polyvinylidene fluoride/polyacrylonitrile (PVDF/PAN) composite grafted with acrylic acid (AA; which form polyacrylic acid (PAA) brush) and decorated with silver (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd) designed for the dechlorination and photodegradation of pesticides was carried out. PAN was used both as a nitrogen dopant as well as a co-polymer. Smooth nanofibers were obtained by electrospinning a solution of 12:2 wt.% PVDF/PAN blend using dimethylformamide (DMF) as solvent. The nanofibers were grafted with AA by free-radical polymerization using 2,2′azobis(2-methylpropionitrile) (AIBN) as initiator. Both bimetallic iron–palladium (Fe–Pd) and titania (TiO₂) nanoparticles (NP) were anchored on the grafted nanofibers via the carboxylate groups by in situ and ex situ synthesis. The Fe–Pd and nitrogen-doped TiO₂ nanoparticles were subsequently used for dechlorination and oxidation of target pollutants (dieldrin, chlorpyrifos, diuron, and fipronil) to benign products. Structural and chemical characterizations of the composites were done using various techniques. These include surface area and porosity analyzer (ASAP) using the technique by Brunner Emmett Teller (BET), Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscope (TEM) analyses were done. After dechlorination, the transformation products (TPs) for dieldrin, chlorpyrifos, diuron, and fipronil were obtained and identified using two-dimensional gas chromatography (time-of-flight) with a mass spectrometer detector (GCxGC-TOFMS). Analysis of total organic carbon (TOC) was carried out and used to extrapolate percentage mineralization. Experimental results showed that dechlorination efficiencies of 96, 93, 96, and 90 % for 1, 2, 2, and 3 h treatment period were respectively achieved for 5 ppm solutions of dieldrin, chlorpyrifos, diuron, and fipronil. The dechlorination of dieldrin, diuron, and fipronil follows first-order kinetics while that of chlorpyrifos followed pseudo-first order. Mineralization performance of 34 to 45 % were recorded when Fe–Pd was used, however upon electrospinning, doping, and grafting (Ag/PAN/PVDF-g-PAA-TiO₂/Fe–Pd composite); it significantly increased to 99.9999 %. This composite reveals great potential for dechlorination and mineralization of pesticides in contaminated water.     

Benchmarking Optical/Thermal Satellite Imagery for Estimating Evapotranspiration and Soil Moisture in Decision Support Tools

Generally, one expects evapotranspiration (ET) maps derived from optical/thermal Landsat and MODIS satellite imagery to improve decision support tools and lead to superior decisions regarding water resources management. However, there is lack of supportive evidence to accept or reject this expectation. We “benchmark” three existing hydrologic decision support tools with the following benchmarks: annual ET for the ET Toolbox developed by the United States Bureau of Reclamation, predicted rainfall‐runoff hydrographs for the Gridded Surface/Subsurface Hydrologic Analysis model developed by the U.S. Army Corps of Engineers, and the average annual groundwater recharge for the Distributed Parameter Watershed Model used by Daniel B. Stephens & Associates. The conclusion of this benchmark study is that the use of NASA/USGS optical/thermal satellite imagery can considerably improve hydrologic decision support tools compared to their traditional implementations. The benefits of improved decision making, resulting from more accurate results of hydrologic support systems using optical/thermal satellite imagery, should substantially exceed the costs for acquiring such imagery and implementing the remote sensing algorithms. In fact, the value of reduced error in estimating average annual groundwater recharge in the San Gabriel Mountains, California alone, in terms of value of water, may be as large as $1 billion, more than sufficient to pay for one new Landsat satellite.     

Comparison of real-time instruments and gravimetric method when measuring particulate matter in a residential building

This study used several real-time and filter-based aerosol instruments to measure PM_2.5 levels in a high-rise residential green building in the Northeastern US and compared performance of those instruments. PM_2.5 24-hr average concentrations were determined using a Personal Modular Impactor (PMI) with 2.5 µm cut (SKC Inc., Eighty Four, PA) and a direct reading pDR-1500 (Thermo Scientific, Franklin, MA) as well as its filter. 1-hr average PM_2.5 concentrations were measured in the same apartments with an Aerotrak Optical Particle Counter (OPC) (model 8220, TSI, Inc., Shoreview, MN) and a DustTrak DRX mass monitor (model 8534, TSI, Inc., Shoreview, MN). OPC and DRX measurements were compared with concurrent 1-hr mass concentration from the pDR-1500. The pDR-1500 direct reading showed approximately 40% higher particle mass concentration compared to its own filter (n = 41), and 25% higher PM_2.5 mass concentration compared to the PMI_2.5 filter. The pDR-1500 direct reading and PMI_2.5 in non-smoking homes (self-reported) were not significantly different (n = 10, R² = 0.937), while the difference between measurements for smoking homes was 44% (n = 31, R² = 0.773). Both OPC and DRX data had substantial and significant systematic and proportional biases compared with pDR-1500 readings. However, these methods were highly correlated: R² = 0.936 for OPC versus pDR-1500 reading and R² = 0.863 for DRX versus pDR-1500 reading. The data suggest that accuracy of aerosol mass concentrations from direct-reading instruments in indoor environments depends on the instrument, and that correction factors can be used to reduce biases of these real-time monitors in residential green buildings with similar aerosol properties.

Implications: This study used several real-time and filter-based aerosol instruments to measure PM_2.5 levels in a high-rise residential green building in the northeastern United States and compared performance of those instruments. The data show that while the use of real-time monitors is convenient for measurement of airborne PM at short time scales, the accuracy of those monitors depends on a particular instrument. Bias correction factors identified in this paper could provide guidance for other studies using direct-reading instruments to measure PM concentrations.     

Assessing and managing intensification in smallholder dairy systems for food and nutrition security in Sub-Saharan Africa

Smallholder farmers play an important part in the dairy value chain in Sub-Saharan Africa. Three technological approaches have been used to improve productivity. These are through, applying agricultural ecological processes (ecological intensification), utilising modern livestock breeding (genetic intensification), and socio-economic intensification. Ecological intensification includes continuous housing of cows applying a cut-and-carry feeding system, introduction of purpose-bred forages and pastures, and the introduction of agro-forestry within the dairy systems. Genetic intensification strategies include: importation of dairy breeds such as Holstein–Friesian (HF) and cross-breeding of the indigenous breeds with HF. Training and capacity-building activities to create sustainable livelihoods have been initiated for farming and technological practices of animal husbandry, but also to enhance appropriate leadership and corporative-building skills that would create and support an enabling environment for sustainability. These improvements and initiatives in the service delivery have been championed by national governments, development partner institutions, or non-governmental organisations through different programmes. Challenges of intensification include matching management to genetic potential of imported and cross-bred improved dairy breeds, ensuring low post-harvest losses, proper utilisation, and reducing environmental impact. Using examples from Kenya, Malawi, Mozambique, Tanzania, and Zambia, this paper reviews the management and assessment approaches used in fostering smallholder dairy development strategies and dairy’s contribution to sustainable livelihoods in the face of intensification.     

Optimal Treatment Zone Moves During Enhanced Reductive Dechlorination in Fractured Bedrock

An enhanced bioremediation pilot test was implemented to study the efficacy of enhancing in situ reductive dechlorination of tetrachloroethene (PCE) in shallow bedrock where some intrinsic degradation to cis‐1,2‐dichloroethene (cis‐1,2‐DCE) was observed without further degradation to vinyl chloride or nontoxic ethene. Limited Dehalococcoides spp. cell concentrations were present within the study area prior to the gravity‐fed injection of an injectate of fermentable carbon substrates in native anaerobic groundwater. Direct connectivity between the injection well screen and performance monitoring well was evidenced and resulted in the degradation of nearly all PCE to cis‐1,2‐DCE, significant decrease in pH, and apparent inhibited Dehalococcoides spp. growth in the study area groundwater in the first six months. After 24 months, nearly all cis‐1,2‐DCE had degraded to nontoxic ethene, pH rebounded to more optimal levels, and abundant growth of Dehalococcoides spp. (6.8E05 cells/mL) and its functional gene expressions responsible for complete dechlorination were evident. The observations indicated initial poor dechlorination within the injection zone did not preclude effective treatment, allowing sufficient monitoring time showed the effective treatment zone (or more‐optimal fringe) first moved outward from the injection zone beyond the monitoring point and then receded back toward the point of injection over a period of two years. ©2015 Wiley Periodicals, Inc.     

A Critique of Estimating Future Costs Using Most Likely Value

ASTM E2137 (Standard Guide for Estimating Monetary Costs and Liability for Environmental Matters, or E2137) is the guidance for developing estimates of future environmental costs. E2137 provides a hierarchy of cost estimation approaches, and expresses an explicit preference for the use of probabilistic cost analysis to develop expected values for environmental costs. Dr. Ram and his colleagues have published an article (Remediation Journal, Autumn 2013) which rejects the use of EV analysis, arguing that while “good in principle” it has little practical value because it is nearly impossible to develop supportable probabilities. The E2137 principles and processes have been used for more than a decade in the context of addressing future environmental costs, yet their view of E2137 renders the standard meaningless. We conclude that the deficiency is not in the ASTM standard, and that when properly constructed, probabilistic analyses can be used to develop expected values with supportable probabilities. ©2015 Wiley Periodicals, Inc.     

Forest carbon management in the United States: 1600-2100

This paper reviews the effects of past forest management on carbon stocks in the United States, and the challenges for managing forest carbon resources in the 21st century. Forests in the United States were in approximate carbon balance with the atmosphere from 1600-1800. Utilization and land clearing caused a large pulse of forest carbon emissions during the 19th century, followed by regrowth and net forest carbon sequestration in the 20th century. Recent data and knowledge of the general behavior of forests after disturbance suggest that the rate of forest carbon sequestration is declining. A goal of an additional 100 to 200 Tg C/yr of forest carbon sequestration is achievable, but would require investment in inventory and monitoring, development of technology and practices, and assistance for land managers.     

Multi-stage sampling for large scale natural resources surveys: a case study of rice and waterfowl

Large-scale sample surveys to estimate abundance and distribution of organisms and their habitats are increasingly important in ecological studies. Multi-stage sampling (MSS) is especially suited to large-scale surveys because of the natural clustering of resources. To illustrate an application, we: (1) designed a stratified MSS to estimate late autumn abundance (kg/ha) of rice seeds in harvested fields as food for waterfowl wintering in the Mississippi Alluvial Valley (MAV); (2) investigated options for improving the MSS design; and (3) compared statistical and cost efficiency of MSS to simulated simple random sampling (SRS). During 2000-2002, we sampled 25-35 landowners per year, 1 or 2 fields per landowner per year, and measured seed mass in 10 soil cores collected within each field. Analysis of variance components and costs for each stage of the survey design indicated that collecting 10 soil cores per field was near the optimum of 11-15, whereas sampling >1 field per landowner provided few benefits because data from fields within landowners were highly correlated. Coefficients of variation (CV) of annual estimates of rice abundance ranged from 0.23 to 0.31 and were limited by variation among landowners and the number of landowners sampled. Design effects representing the statistical efficiency of MSS relative to SRS ranged from 3.2 to 9.0, and simulations indicated SRS would cost, on average, 1.4 times more than MSS because clustering of sample units in MSS decreased travel costs. We recommend MSS as a potential sampling strategy for large-scale natural resource surveys and specifically for future surveys of the availability of rice as food for waterfowl in the MAV and similar areas.