Novel polyol initiator from polyurethane recycling residue

Flexible polyurethane foams can be advantageously treated by two-phase glycolysis in order to recover polyols with improved quality. The bottom phase obtained, which contains highly toxic reaction by-products and the excess glycol, presents an environmental and economic problem which should be solved. The main purpose of this work is the development of process for the valorization of these by-products, converting them in non-dangerous and profitable substances. For this process, most of the glycol can be recovered by means of vacuum distillation in order to reuse it in the glycolysis. On the other hand, the vacuum residue, containing the isocyanate part of the glycolysis by-products, was assayed as initiator in the synthesis of new polyols. Propoxylation of the initiator was carried out in different experimental conditions to obtain several polyether-polyols. Rigid polyurethane foams with suitable technical properties were synthesized with those polyols synthesized with the dangerous glycolysis by-products.     

Unexpected effects of sublethal doses of insecticide on the peripheral olfactory response and sexual behavior in a pest insect

Pesticides have long been used as the main solution to limit agricultural pests, but their widespread use resulted in chronic or diffuse environmental pollutions, development of insect resistances, and biodiversity reduction. The effects of low residual doses of these chemical products on organisms that affect both targeted species (crop pests) but also beneficial insects became a major concern, particularly because low doses of pesticides can induce unexpected positive—also called hormetic—effects on insects, leading to surges in pest population growth at greater rate than what would have been observed without pesticide application. The present study aimed to examine the effects of sublethal doses of deltamethrin, one of the most used synthetic pyrethroids, known to present a residual activity and persistence in the environment, on the peripheral olfactory system and sexual behavior of a major pest insect, the cotton leafworm Spodoptera littoralis. We highlighted here a hormetic effect of sublethal dose of deltamethrin on the male responses to sex pheromone, without any modification of their response to host-plant odorants. We also identified several antennal actors potentially involved in this hormetic effect and in the antennal detoxification or antennal stress response of/to deltamethrin exposure.     

Building capacity through action research: reflections on working with low-carbon communities in the UK

This paper describes a four-year programme of “action research” (AR) undertaken with six communities in the UK, referred to as the Evaluating Low-Carbon Communities (EVALOC) project. The research combined a programme of research events with phased household-level monitoring of energy and carbon-reduction interventions. The carbon-reduction interventions were funded by the UK’s Department of Energy and Climate Change prior to the onset of the research. AR has recently been adopted within the context of environmental behaviour change programmes in the UK, with a number of methodological challenges. The EVALOC project’s challenges included developing a collaborative research design; building reciprocity between the researchers and research participants; dealing with biases and burdens in the research process; ensuring analytical rigour in the interpretation of the primarily qualitative evidence and dealing with the long-term and process-driven outcomes that arise from such interactions. This paper explores and discusses the challenges of AR in relation to selected research outcomes from EVALOC. We conclude by suggesting that the AR approach has helped to build capacity in the participating low-carbon communities (LCCs), through supporting the design, delivery and evaluation of their energy and carbon-reduction activities.     

Health risks of environmental exposure to metals and herbicides in the Pardo River,Brazil

Mixture of metals and herbicides in rivers may pose relevant risks for the health of surrounding communities. Humans may be exposed to river pollution through intake of contaminated water and fish, as well as irrigated agricultural products. The aim of this study was to assess the human health risks of environmental exposure to metals and herbicides through water and fish intake in the Pardo River. Metals (Al, As, Be, Cd, Cr, Cu, Pb, Mn, Hg, Ni, Tl, Sn, V, and Zn) were analyzed in river water and in edible fish. Herbicides (ametryn, atrazine, diuron, hexazinone, simazine, and tebuthiuron) were analyzed in river water. Seasonal variances were also studied. Aluminum, Cd, Cu, Mn, Pb, and Zn levels in river water were higher than the USEPA benchmarks. Non-carcinogenic risks due to pollutants mixture exposure were above the limit, and carcinogenic risks of As exposure were >10^?6 in the sampling points during the rainy season. Metal levels in fish were lower than the Brazilian legislation and do not pose a threat to public health. Herbicides were detected in four sampling points, with atrazine concentrations (range 0.16–0.32 μg/L) below the Brazilian standard (2.0 μg/L), but above the European Union standard (0.1 μg/L). Considering the water supply needs of cities located in the Pardo River Basin and the persistence of metals and herbicides, the present study indicated that there was a seasonal influence on non-carcinogenic and carcinogenic risks to human health, especially in the rainy season. Studies for water treatment plants implantation should consider the risks of exposure to persistent substances, in order to protect the population.     

Bulk atmospheric deposition of persistent toxic substances (PTS) along environmental gradients in Brazil

Bulk atmospheric deposition measurements for selected persistent toxic substances (PTS) were performed along environment gradients (urban–suburban–rural–background sites) in Brazil. The aim with this work is to investigate the fate of PTS and their emissions in South America, particularly along environment transects. Bulk sampler systems (polyurethane foams, 1?×?1 m²) were fixed along environment gradients (urban–suburban–rural–background) over summer and winter periods (2005–2007) at sites of different climate zones of Brazil. Organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) were analyzed by gas chromatography coupled to electron capture detector (Shimadzu 2010, 20i GC-ECD). Urban sites reported the highest deposition rates for all PTS, ranging from tens to thousands of pictograms per square meter per day. Basically, there were no obvious seasonal differences in deposition rate concentrations for PTS along the urban–suburban–rural–background gradient. Dichlorodiphenyltrichloroethane (DDT) and its metabolites were the OCs most frequently detected at relatively high deposition rate levels (>1,000 pg m^?2 day^?1). Other legacy and current-use pesticides such as hexachlorocyclohexanes, endosulfans, hexachlorcyclobenzine, dieldrin, aldrin, metoxichlor, and chlodanes were also detected at lower deposition rate levels (10–100 pg m^?2 day^?1). PCBs were detected at extremely high deposition rate levels (1,000–10,000 pg m^?2 day^?1) with highest contributions from the tetra-PCBs (PCB-52, PCB-44, PCB-66, PCB-81, and PCB-77) and penta-PCB congeners (PCB-101, PCB-105, PCB-114, PCB-118, and PCB-126). The greatest deposition rate concentrations for total PCBs were mainly detected at urban sites in connection with high population densities. The observed high deposition rate concentrations for PCBs and DDTs at urban sites are probably associated with old PTS stocks emissions. For PCBs in particular, the high levels are strongly associated with local population densities, highlighting the effect of local/regional urban sources on these target PTS. These results are important to show that even though the use of PTS is regulated, the deposition of selected PTS is still impacted by local and regional emissions in Brazil and may be related to the historical and continued emissions from old PTS stocks.     

Application of Fenton, photo-Fenton, solar photo-Fenton, and UV/H2O2 to degradation of the antineoplastic agent mitoxantrone and toxicological evaluation

In the present study, selected advanced oxidation processes (AOPs)—namely, photo-Fenton (with Fe²⁺, Fe³⁺, and potassium ferrioxalate—FeOx—as iron sources), solar photo-Fenton, Fenton, and UV/H₂O₂—were investigated for degradation of the antineoplastic drug mitoxantrone (MTX), frequently used to treat metastatic breast cancer, skin cancer, and acute leukemia. The results showed that photo-Fenton processes employing Fe(III) and FeOx and the UV/H₂O₂ process were most efficient for mineralizing MTX, with 77, 82, and 90 % of total organic carbon removal, respectively. MTX probably forms a complex with Fe(III), as demonstrated by voltammetric and spectrophotometric measurements. Spectrophotometric titrations suggested that the complex has a 2:1 Fe³⁺:MTX stoichiometric ratio and a complexation constant (K) of 1.47 × 10⁴ M^–1, indicating high MTX affinity for Fe³⁺. Complexation partially inhibits the involvement of iron ions and hence the degradation of MTX during photo-Fenton. The UV/H₂O₂ process is usually slower than the photo-Fenton process, but, in this study, the UV/H₂O₂ process proved to be more efficient due to complexing of MTX with Fe(III). The drug exhibited no cytotoxicity against NIH/3T3 mouse embryonic fibroblast cells when oxidized by UV/H₂O₂ or by UV/H₂O₂/FeOx at the concentrations tested.     

Participant-based monitoring of indoor and outdoor nitrogen dioxide,volatile organic compounds,and polycyclic aromatic hydrocarbons among MICA-Air households

The Mechanistic Indicators of Childhood Asthma (MICA) study in Detroit, Michigan introduced a participant-based approach to reduce the resource burden associated with collection of indoor and outdoor residential air sampling data. A subset of participants designated as MICA-Air conducted indoor and outdoor residential sampling of nitrogen dioxide (NO₂), volatile organic compounds (VOCs), and polycyclic aromatic hydrocarbons (PAHs). This participant-based methodology was subsequently adapted for use in the Vanguard phase of the U.S. National Children’s Study. The current paper examines residential indoor and outdoor concentrations of these pollutant species among health study participants in Detroit, Michigan.Pollutants measured under MICA-Air agreed well with other studies and continuous monitoring data collected in Detroit. For example, NO₂ and BTEX concentrations reported for other Detroit area monitoring were generally within 10–15% of indoor and outdoor concentrations measured in MICA-Air households. Outdoor NO₂ concentrations were typically higher than indoor NO₂ concentration among MICA-Air homes, with a median indoor/outdoor (I/O) ratio of 0.6 in homes that were not impacted by environmental tobacco smoke (ETS) during air sampling. Indoor concentrations generally exceeded outdoor concentrations for VOC and PAH species measured among non-ETS homes in the study. I/O ratios for BTEX species (benzene, toluene, ethylbenzene, and m/p- and o-xylene) ranged from 1.2 for benzene to 3.1 for toluene. Outdoor NO₂ concentrations were approximately 4.5 ppb higher on weekdays versus weekends. As expected, I/O ratios pollutants were generally higher for homes impacted by ETS.These findings suggest that participant-based air sampling can provide a cost-effective alternative to technician-based approaches for assessing indoor and outdoor residential air pollution in community health studies. We also introduced a technique for estimating daily concentrations at each home by weighting 2- and 7-day integrated concentrations using continuous measurements from regulatory monitoring sites. This approach may be applied to estimate short-term daily or hourly pollutant concentrations in future health studies.     

Is Daily Mortality Associated Specifically with Fine Particles? Data Reconstruction and Replication of Analyses

ABSTRACT

In 1996, Schwartz, Dockery, and Neas¹ reported that daily mortality was more strongly associated with concentrations of PM_2.5 than with concentrations of larger particles (coarse mass [CM]) in six U.S. cities (“original paper'V'original analyses”). Because of the public policy implications of the findings and the uniqueness of the concentration data, we undertook a reanalysis of these results. This paper presents results of the reconstruction of these data and replication of the original analyses using the reconstructed data. The original investigators provided particulate air pollution data for this paper. Daily weather and daily counts of total and cause-specific deaths were reconstructed from original public records. The reconstructed particulate air pollution and weather data were consistent with the summaries presented in the original paper. Daily counts of deaths in the reconstructed data set were lower than in the original paper because of restrictions on residence and place of death. The reconstruction process identified an administrative change in county codes that led to higher numbers of deaths in St. Louis. Despite these differences in daily counts of deaths, the estimated effects of par-ticulate air pollution from the reconstructed dataset, using analytic methods as described in the original paper, produced combined effect estimates essentially equivalent to the originally published results. For example, the estimated association of a 10 |j.g/m³ increase in 2-day mean particulate air pollution on total mortality was 1.3% (95% confidence interval [CI] 0.9-1.7%, t = 6.53) for PM₂₅ based on the reconstructed dataset, compared to the originally reported association of 1.5% (95% CI 1.1-1.9%, t = 7.41). For coarse particles, the estimated association from the reconstructed dataset was 0.4% (95% CI -0.2-0.9%, t = 1.43) compared to the originally reported association of 0.4% (95% CI -0.1-1.0%, t = 1.48). These results from the reconstructed data suggest that the original results reported by Schwartz, Dockery, and Neas¹ were essentially replicated.     

Measurements and modeling of reactive nitrogen deposition in southeast Brazil

Increased reactive nitrogen (N_r) deposition due to expansion of agro-industry was investigated considering emission sources, atmospheric transport and chemical reactions. Measurements of the main inorganic nitrogen species (NO₂, NH₃, HNO₃, and aerosol nitrate and ammonium) were made over a period of one year at six sites distributed across an area of ∼130,000 km² in southeast Brazil. Oxidized species were estimated to account for ∼90% of dry deposited N_r, due to the region’s large emissions of nitrogen oxides from biomass burning and road transport. NO₂-N was important closer to urban areas, however overall HNO₃-N represented the largest component of dry deposited N_r. A simple mathematical modeling procedure was developed to enable estimates of total N_r dry deposition to be made from knowledge of NO₂ concentrations. The technique, whose accuracy here ranged from <1% to 29%, provides a useful new tool for the mapping of reactive nitrogen deposition.     

Review of biosolids management options and co-incineration of a biosolid-derived fuel

This paper reviews current biosolids management options, and identifies incineration as a promising technology. Incineration is attractive both for volume reduction and energy recovery. Reported emissions from the incineration of biosolids were compared to various regulations to identify the challenges and future direction of biosolids incineration research. Most of the gaseous and metal emissions were lower than existing regulations, or could be met by existing technologies. This paper also presents the results of an experimental study to investigate the potential use of biosolids for co-incineration with wood pellets in a conventional wood pellet stove. Pilot scale combustion tests revealed that co-incineration of 10% biosolids with 90% premium grade wood pellets resulted in successful combustion without any significant degradation of efficiency and emissions.