Selectivity of Nano Zerovalent Iron in In Situ Chemical Reduction: Challenges and Improvements

Nano zerovalent iron (nZVI) is a promising remediation technology utilizing in situ chemical reduction (ISCR) to clean up contaminated groundwater at hazardous waste sites. The small particle size and large surface area of nZVI result in high reactivity and rapid destruction of contaminants. Over the past 20 years, a great deal of research has advanced the nZVI technology from bench‐scale tests to field‐scale applications. However, to date, the overall number of well‐characterized nZVI field deployments is still small compared to other alternative remedies that are more widely applied. Apart from the relatively high material cost of nZVI and questions regarding possible nanotoxicological side effects, one of the major obstacles to the widespread utilization of nZVI in the field is its short persistence in the environment due to natural reductant demand (NRD). The NRD for nZVI is predominantly due to reduction of water, but other reactions with naturally present oxidants (e.g., oxygen) occur, resulting in situ conditions that are reducing (high in ferrous iron phases and H₂) but with little or no Fe(0). This article reviews the main biogeochemical processes that determine the selectivity and longevity of nZVI, summarizes data from prior (laboratory and field) studies on the longevity of various common types of nZVI, and describes modifications of nZVI that could improve its selectivity and longevity for full‐scale applications of ISCR. © 2016 Wiley Periodicals, Inc.     

Analysis of temporal and spatial dichotomous PM air samples in the El Paso-Cd. Juarez air quality basin.

This paper presents and discusses the results obtained from the gravimetric and chemical analyses of the 24-hr average dichotomous samples collected from five sites in the El Paso-Cd. Juarez air quality basin between August 1999 and March 2000. Gravimetric analysis was performed to determine the temporal and spatial variations of PM2.5 (particulate matter less than 2.5 microm in diameter) and PM25-10 (particulate matter less than 10 pm but greater than 2.5 microm in diameter) mass concentrations. The results indicate that approximately 25% of the PM10 (i.e., PM25 + PM25-10) concentration is composed of PM2.5. Concurrent measurements of hourly PM concentrations and wind speed showed strong diurnal patterns of the regional PM pollution. Results of X-ray fluorescence (XRF) elemental analyses were compared to similar but limited studies performed by the Texas Natural Resource Conservation Commission (TNRCC) in 1990 and 1997. Major elements from geologic sources-Al, Si, Ca, Na, K, Fe, and Ti-accounted for 35% of the total mass concentrations in the PM2.5-10 fraction, indicating that geologic sources in the area are the dominant PM sources. Levels of toxic trace elements, mainly considered as products of anthropogenic activities, have decreased significantly from those observed in 1990 and 1997.     

Relationship between antibiotic residues and occurrence of resistant bacteria in Nile tilapia (Oreochromisniloticus) cultured in cage-farm

The aim of this study was to investigate the relationship between antibiotic residues found in the muscle of cage-farm-raised Nile tilapia (Oreochromisniloticus), the occurrence of resistant bacteria, and the sanitary practices adopted by farmers in Ilha Solteira reservoir, Brazil. Nine fish (three small fish, 40–200 g; three medium-sized fish, 200–500 g; and three large fish, 500–800 g) were collected from four cage farms every three months from April 2013 to January 2014. Ten antibiotic residues were determined using liquid chromatography-mass spectrometry, and bacteria were isolated and tested for antibiotic resistance to determine the multiple antibiotic resistance (MAR) index. Only three antibiotics (oxytetracycline, tetracycline, and florfenicol) were detected in the muscle of Nile tilapia, and their residues were the highest in small fish; however, the MAR index was higher in large fish. In addition, a direct positive relationship between the MAR index and the concentration of antibiotic residues in Nile tilapia was found. Overall, the adoption of prophylactic management practices improved the sanitary status of cage farms, reducing bacterial infections and hampering the development of antibiotic-resistant bacteria.     

Commodity production as restoration driver in the Brazilian Amazon? Pasture re-agro-forestation with cocoa (<Emphasis Type="Italic">Theobroma cacao</Emphasis>) in southern Pará

The increasing demand for agricultural commodities is a major cause of tropical deforestation. However, pressure is increasing for greater sustainability of commodity value chains. This includes the demand to establish new crop plantations and pasture areas on already deforested land so that new forest clearing for agriculture is minimized. Where tree crops are planted as part of agroforestry systems on deforested land, this amounts to a form of re-agro-forestation which can generate environmental benefits in addition to crop production. Here, we discuss a case where agroforestry systems based on cocoa (Theobroma cacao) are being established on crop and pasture land in the south of Pará state, Brazilian Amazon. The adoption of cocoa by farmers and ranchers of the region is stimulated by the coincidence of (1) favorable prospects for cocoa on the national and international markets including the expectation of a global cocoa supply gap; (2) environmental policies obliging land owners to reforest excess cleared land with native trees, with agroforests based on the native cocoa tree being an economically attractive option; and (3) biophysical conditions (especially soil fertility) favorable for growing cocoa in part of the region. We show that in the state of Pará at least 1.26 million hectares of naturally high-fertility soils in deforested areas outside legally protected and indigenous lands are potentially suitable for cocoa production with low agrochemical inputs, sufficient to make a significant contribution to closing the predicted supply gap. Their actual suitability depends on their state of degradation after years of pasture use and the availability of technologies and finance to convert them into tree crop agroforests. We discuss the significant environmental benefits of pasture re-agro-forestation with cocoa-based systems, including reduced emissions of up to 135 Mg of carbon per hectare compared to the historically common scenario of planting cocoa after forest clearing. We identify important research questions related to the scaling up of this practice and the maximization of its environmental benefits. We conclude that the coincidence of the afore-mentioned factors could drive a re-agro-forestation frontier in this part of the Amazon, with potential for positive outcomes in terms of commodity production while generating social and environmental benefits.     

A data envelopment analysis approach to choose transport modes based on eco-efficiency

The main purpose of this paper is to use data envelopment analysis (DEA) as a support tool to establish a relative eco-efficiency measure for the different bioethanol transportation modes and to prioritize these different modes according to these figures. From a review of previous studies, we selected a set of attributes to be considered in DEA, and then experts were consulted about the importance of these attributes for this type of analysis in Brazil. To quantify the attributes, we established indicators and submitted them to DEA to evaluate the relative eco-efficiency to each available transportation mode for the case studied. The use of DEA established the guidelines to improve the transportation modes that were not considered 100?% relatively eco-efficient. These improvements could be achieved considering the percentage, reduction or growth for each of the attributes in the selected transportation mode. The proposed approach can help the Brazilian government to develop a plan to improve the bioethanol transportation infrastructure and can be used to propel short-term improvements in the highway transport of bioethanol, which could be useful given the Brazilian transportation context.     

Biodegradation of Poly(3-Hydroxybutyrate) Produced from Cupriavidus necator with Different Concentrations of Oleic Acid as Nutritional Supplement

The environmental impact caused by the disposal of plastics has motivated the development of biodegradable materials. Recent studies showed that supplementation with oleic acid (OA) in cultures producing poly(3-hydroxybutyrate), P(3HB), increased the polymer productivity. However only few studies have shown the properties and biodegradation profile of the polymer obtained. This research investigated the influence of OA concentration on the biodegradation of the P(3HB) obtained from cultures of Cupriavidus necator. The crystallinity of the casting films determined by differential scanning calorimetry (DSC) was reduced from 70% (0 g L⁻¹ of OA) to 52% (3.0 g L⁻¹ of OA). A reduction of 11 °C in the melting temperature was observed with 3.0 g L⁻¹ of OA. The kinetic of biodegradation was: 3.0 > 1.5 > 0.9 > 0.3 > 0 g L⁻¹ of OA.     

Inferring episodic atmospheric iron fluxes in the Western South Atlantic

Iron (Fe) and other trace elements such as Zn, Mn, Ni and Cu are known as key-factors in marine biogeochemical cycles. It is believed that ocean primary productivity blooms in iron deficient regions can be triggered by iron in aeolian dust. Up to now, scarce aerosol elemental composition, based on measurements over sea at the Western South Atlantic (WSA), exist. An association between the Patagonian semi-desert dust/Fe and chlorophyll-a variability at the Argentinean continental shelf is essentially inferred from models. We present here experimental data of Fe enriched aerosols over the WSA between latitudes 22°S–62°S, during 4 oceanographic campaigns between 2002 and 2005. These data allowed inferring the atmospheric Fe flux onto different latitudinal bands which varied from 30.4 to 1688 nmolFe m^?2 day^?1 (October 29th–November 15th, 2003); 5.83–1586 nmolFe m^?2 day^?1 (February 15th–March 6th, 2004) and 4.73–586 nmolFe m^?2 day^?1(October 21st–November 5th, 2005).     

Leachable 226Ra in Philippine phosphogypsum and its implication in groundwater contamination in Isabel, Leyte, Philippines

Phosphogypsum (PG), the major waste material in phosphate fertilizer processing, has been known to contain enhanced levels of naturally-occurring radionuclides especially (226)Ra.The lack of radioactivity data regarding Philippine phosphogypsum and its environmental behavior in the Philippine setting has brought concern on possible contamination of groundwater beneath the phosphogypsum ponds in Isabel, Leyte, Philippines. The radioactivity of Philippine phosphogypsum was determined and the leaching of (226)Ra from phosphogypsum and through local soil was quantified. Level of (226)Ra in groundwater samples in Isabel, Leyte, Philippines was also quantified to address the primary concern. It was found that the (226)Ra activity in Philippine phosphogypsum is distributed in a wide range from 91.5 to 935 Bq/kg. As much as 5% of (226)Ra can be leached from Philippine PG with deionized water. In vitro soil leach experiments suggest that the soil in the phosphate fertilizer plant area would be able to deter the intrusion of (226)Ra into the water table. Compared to reported values of natural groundwater levels of (226)Ra, the concentration of this radionuclide in Isabel, Leyte groundwater suggest that there is no (226)Ra intrusion brought about by the presence of phosphogypsum ponds in the area.     

Assessment of polycyclic aromatic hydrocarbon influx and sediment contamination in an urbanized estuary

Sediments from the Patos Lagoon Estuary in Southern Brazil and sludge from incoming effluents were assessed for the distribution of polycyclic aromatic hydrocarbons (PAHs). Shallow sediments adjoining the City of Rio Grande were found to be contaminated by PAHs mainly near urban effluent discharge, as well as in the port area. Effluents clustered into four groups according to their sources (sewage, industrial, runoff, and mixed), with each demonstrating different contributions of PAHs to the estuary. There was a predominance of runoff and mixed sources. Navigation activity was the second most important source of PAHs to sediments. The PAHs ratio identified the origin of these contaminants as essentially pyrolytic. The impact of PAHs as a result of uncontrolled disposal or accidental discharge of PAH-rich residues was suggested for several points. These points were primarily near gas stations and motor workshops. In about 30% of sampled sediments, the concentration of benzo[a]pyrene surpassed the Threshold Effects Level adopted for marine environments.     

Evaluation of the best compromise between the urban air quality monitoring resolution by diffusive sampling and resource requirements

The need to collect data representative of overall urban pollution is all-important in order to monitor the population exposure. High spatial resolution monitoring using diffusive samplers allows studying of the urban pollutant distribution, thus enabling deeper investigation of their generation and diffusion mechanisms. Nevertheless, such a monitoring campaign has a certain cost. In this study we point out how to find the best compromise between the number of necessary measurements and the affordable costs for monitoring campaigns. We also describe an innovative method for the proper design of a fixed urban monitoring network by means of preliminary high spatial resolution campaigns using diffusive samplers. Four European capital cities (Dublin, Madrid, Paris and Rome) were monitored six times, each time for seven days. Benzene, toluene, ethylbenzene, xylenes (BTEX) and NO(2) concentrations were measured at 146 sites in Dublin, 293 in Madrid, 339 in Paris and 290 in Rome. Multiscale grids have been drawn which ranged in mesh size from 500 m to 2 km. The statistical processing of data produced a twofold result: the creation of isoconcentration maps with geostatistical procedures, and an algorithm aimed at locating the minimum number of sampling sites where the fixed monitoring stations should be placed. Average urban levels estimated on the basis of these selected sites differ by less than 8% from those calculated on the whole populations of the sampled points. The aim of this work is to investigate how far the resolution of a monitoring campaign of urban pollution by diffusive sampling can be reduced, thus making the monitoring less expensive in terms of human and financial resources, while preserving the same quality of the results that could be achieved with a higher resolution. We found that there is no significant loss of information when the resolution of the monitoring grid for BTEX is lowered to a mesh size of 1.85 km, that is a sampling site each 3.4 km(2), and that the minimum number of sampling sites to be used is N = 0.29 A, where A is the urban surface to be monitored (in km(2)). As the spatial distribution of NO(2) is less sensitive to the distance from the emission source than that of BTEX, this relationship could be retained as a valid lower limit for the mesh grid size also for NO(2) monitoring.