Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

An Integrated Assessment of Climate Change and the Accelerated Introduction of Advanced Energy Technologies - An Application of MiniCAM 1.0

We report results from the application of an integrated assessment model, MiniCAM 1.0. The model is employed to explore the full range of climate change implications of the successful development of cost effective, advanced, energy technologies. These technologies are shown to have a profound effect on the future magnitude and rate of anthropogenic climate change. We find that the introduction of assumptions developed by a group of ‘bottom-up’ modelers for the LEESS scenarios into a ‘top-down’ model, the Edmonds-Reilly-Barns Model, leads to ‘top down’ emissions trajectories similar to those of the LEESS. The cumulative effect of advanced energy technologies is to reduce annual emissions from fossil fuel use to levels which stabilize atmospheric concentrations below 550 ppmv. While all energy technologies play roles, the introduction of advanced biomass energy production technology is particularly important. The consideration of all greenhouse related anthropogenic emissions, and in particular sulfur dioxide, is found to be important. We find that the consideration of sulfur dioxide emissions coupled to rapid reductions in carbon dioxide emissions leads to higher global mean temperatures prior to 2050 than in the reference case. This result is due to the short-term cooling impact of sulfate aerosols, which dominates the long-term warming impact of CO₂ and CH₄ in the years prior to 2050. We also show that damage calculations which use only mean global temperature and income may be underestimating damages by up to a factor of five. Disaggregating income reduces this to a factor of two, still a major error. Finally, the role of the discount rate is shown to be extraordinarily important to technology preference.     

Effects of aeration frequency on leachate quality and waste in simulated hybrid bioreactor landfills

Research has been conducted to investigate the effects of daily aeration frequency on leachate quality and waste settlement in simulated hybrid landfill bioreactors. Four laboratory-scale reactors were constructed and operated for about 10 months to simulate different bioreactor operations, including one anaerobic bioreactor and three hybrid bioreactors with different aeration frequencies (one, two, and four times per day). Chemical oxygen demand (COD) and biochemical oxygen demand (BOD₅) reduced more than 96% of the initial concentrations in all aerated bioreactors. The differences of COD and BOD₅ reductions among tested aeration frequencies were relatively small. For ammonia nitrogen, the higher aeration frequency (two or four times per day) resulted in the quicker reduction. Overall, the concentrations of heavy metals (Cr, Co, Cu, Mn, Ni, and Zn) decreased over time except Cd and Pb. The reduction of redox-sensitive metal concentrations (Mn, Co, Ni, and Cu) was greater in aerated bioreactors than in anaerobic bioreactor. Settlement of municipal solid waste (MSW) was enhanced with higher frequency of aeration events (four times per day).

Implications: In recent years, hybird bioreactor landfill technology has gained a lot of attention. Appropriate aeration rate is crucial for hybrid bioreactor operation, but few studies have been done and different results were obtained. Research was conducted to investigate the effects of daily aeration frequency on leachate quality and waste settlement. Results indicated that aeration can effectively accelerate waste stabilization and remove organic carbon concentration and total nitrogen in the leachate.     

Characterizing Drought in Irrigated Agricultural Systems: The Surface Water Delivery Index (SWDI)

Quantifying surface water shortages in arid and semiarid agricultural regions is challenging because limited water supplies are distributed over long distances based on complex water management systems constrained by legal, economic, and social frameworks that evolve with time. In such regions, the water supply is often derived in a climate dramatically different from where the water is diverted to meet agricultural demand. The existing drought indices which rely on local climate do not portray the complexities of the economic and legal constraints on water delivery. Nor do these indices quantify the shortages that occur in drought. Therefore, this research proposes a methodological approach to define surface water shortages in irrigated agricultural systems using a newly developed index termed the Surface Water Delivery Index (SWDI). The SWDI can be used to uniformly quantify surface water deficits/shortages at the end of the irrigation season. Results from the SWDI clearly illustrate how water shortages in droughts identified by the existing indices (e.g., SPI and PDSI) vary strongly both within and between basins. Some surface water entities are much more prone to water shortages than other entities based both on their source of water supply and water right portfolios.     

Case study of landfill leachate recirculation using small-diameter vertical wells

A case study of landfill liquids addition using small diameter (5 cm) vertical wells is reported. More than 25,000 m³ of leachate was added via 134 vertical wells installed 3 m, 12 m, and 18 m deep over five years in a landfill in Florida, US. Liquids addition performance (flow rate per unit screen length per unit liquid head) ranged from 5.6 × 10^?8 to 3.6 × 10^?6 m³ s^?1 per m screen length per m liquid head. The estimated radial hydraulic conductivity ranged from 3.5 × 10^?6 to 4.2 × 10^?4 m s^?1. The extent of lateral moisture movement ranged from 8 to 10 m based on the responses of moisture sensors installed around vertical well clusters, and surface seeps were found to limit the achievable liquids addition rates, despite the use of concrete collars under a pressurized liquids addition scenario. The average moisture content before (51 samples) and after (272 samples) the recirculation experiments were 23% (wet weight basis) and 45% (wet weight basis), respectively, and biochemical methane potential measurements of excavated waste indicated significant (p < 0.025) decomposition.     

A comparison study on high-temperature water–gas shift reaction over Fe/Al/Cu and Fe/Al/Ni catalysts using simulated waste-derived synthesis gas

A comparative study on Fe/Al, Fe/Al/Cu, and Fe/Al/Ni catalysts in high-temperature water–gas shift reaction (HT–WGS) using simulated waste-derived synthesis gas has been carried out. The metal oxide (Cu and Ni) and aluminum incorporated Fe catalysts were designed to get highly active HT–WGS catalysts. Despite the high CO concentration in the simulated waste-derived synthesis gas, Fe/Al/Cu catalyst exhibited the highest CO conversion (84 %) and 100 % selectivity to CO₂ at a very high gas hourly space velocity (GHSV) of 40,057 h^?1. The outstanding catalytic performance is mainly due to easier reducibility, the synergy effect of Cu and Al, and the stability of the magnetite.     

Properties of alkali-activated systems with stone powder sludge

This article investigates the effects of stone powder sludge on the microstructure and strength development of alkali-activated fly ash and blast furnace slag mixes. Stone powder sludge produced from a crushed aggregate factory was used to replace fly ash and granulated blast furnace slag at replacement ratios of 0%, 10%, 20%, and 30% by mass. The unit weight and compressive strength of the samples were measured, and scanning electron microscopy/energy dispersive spectroscopy and X-ray diffraction (XRD) analyses were performed. The test results indicated that the compressive strength of alkali-activated blast furnace slag mixes using stone powder sludge was higher than that of the alkali-activated blast furnace slag control mix, but the compressive strength of alkali-activated fly ash mixes decreased with increasing replacement ratio of stone powder sludge. Microscopy results indicated that for alkaliactivated blast furnace slag samples, broken surfaces were more evident than for the alkali-activated fly ash samples. For all XRD diagrams, broad and diffuse peaks were observed around 2θ = 35° (d = 2.96–3.03 Å), implying amorphous or short-ordering structure phases.     

An assessment of dust, endotoxin, and microorganism exposure during waste collection and sorting

This study was conducted to assess inhalation exposure to dust, endotoxin, and microorganisms (including viable bacteria, Gram-negative bacteria [GNB], and fungi) during waste collection and sorting; to identify factors affecting this exposure; and to estimate the gastrointestinal exposure to microorganisms. A total of 48 or 49 workers involved in collecting and sorting waste from households or the street were studied. Each worker carried two personal samplers in which filters were placed in the breathing zone for estimation of inhalation exposure. To assess the possibility of gastrointestinal exposure, microorganisms on the workers' faces were collected before and after work and compared with those collected from office workers. Inhalation exposure levels were categorized according to job title, waste type handled, and working conditions and were compared using analysis of variance. Multiple regression models were developed to identify those factors that substantially affected inhalation exposure. The average exposure level to total dust was 0.9 mg/m3 (range = 0.05 to 4.51 mg/m3), and the average exposure to endotoxin was 1123 EU/m3. The average respective exposure levels to bacteria, GNB, and fungi each exceeded 10(4) colony forming units (CFU)/m3. The multiple regression models found several factors that significantly explained the variation in levels of inhalation exposure to endotoxin and microorganisms; namely, sex (dust, bacteria, and GNB), job title (GNB and fungi), collection day (dust, bacteria, and GNB), temperature (endotoxin and GNB), humidity (endotoxin and fungi), and region (endotoxin) were significantly associated with exposure to these agents. In addition, the workers' faces were highly contaminated with microorganisms. In conclusion, inhalation exposure to endotoxin and microorganisms was high during waste collection and sorting, which may place workers at risk of developing various health problems, including respiratory complaints.     

Sorption and Biodegradation of Vapor-Phase Organic Compounds with Wastewater Sludge and Food Waste Compost

ABSTRACT

To test the possible use of composted food waste and wastewater sludge as biofilters to treat gas-phase volatile organic compounds (VOCs), batch experiments were conducted with an isolated strain that could degrade aromatic compounds under aerobic conditions. A benzene and trichloroethylene (TCE) mixture was used as the gas-phase pollutant in experiments with composted food waste, sludge, and soil. Under aerobic conditions, benzene was degraded as a primary substrate and TCE was degraded cometabolically, with water contents varying from 6 to 60% (volume of water added/volume of solid). Optimal water content for VOC removal was 12% for the soil, 36% for the composted food waste, and 48% for the sludge.

The extent of VOC sorption and biodegradation at the optimal water content was different for each material. With the same initial VOC concentration, more VOCs were removed by sorption onto the composted food waste and the sludge, while less VOCs were biodegraded in comparison with the results using soil. The reason the biodegradation in the soil was greater may be partly attributed to the fact that, due to less sorption, the aqueous-phase concentration of VOCs, which microorganisms could utilize as a carbon source or cometabolize, was higher. We also speculate that the distribution of microorganisms in each medium affects the rate of biodegradation. A large number of microorganisms were attached to the composted food waste and sludge. Mass transfer of VOCs and oxygen to these microorganisms, which appear to have been heterogeneously distributed in clusters, may have been limited, resulting in hindered biodegradation.     

Ozone Artifacts and Carbonyl Measurements Using Tenax GR,Tenax TA,Carbopack B,and Carbopack X Adsorbents

Abstract

Four popular thermally desorbable adsorbents used for air sampling (Tenax TA, Tenax GR, Carbopack B, and Carbopack X) are examined for the potential to form artifacts with ozone (O₃) at environmental concentrations. The performance of these adsorbents for the ketone and alde-hyde species identified as O₃-adsorbent artifacts was also characterized, including recovery, linearity, and method detection limits (MDLs). Using gas chromatography/mass spectrometry, 13 different artifacts were identified and confirmed for both Tenax TA and Tenax GR, 9 for Carbopack B, but none for Carbopack X. Several O₃ artifacts not reported previously were identified, including: pentanal, 3-hexanone, 2-hexanone, hexanal, 3-heptanone, and heptanal with Tenax TA; pentanal, 3-hexanone, 2-hexanone, hexanal, and 3-heptanone on Tenax GR; and 1-octene and 1-nonene with Carbopack B. Levels of straight-chain aldehyde artifacts rapidly diminished after a few cycles of adsorbent conditioning/O₃ exposure, and concentrations could be predicted using a first-order model. Phenyl-substituted carbonyl artifacts (benzalde-hyde and acetophenone) persisted on Tenax TA and GR even after 10 O₃ exposure-conditioning cycles. O₃ breakthrough through the adsorbent bed was most rapid in adsorbents that yielded the highest levels of artifacts. Overall, artifact composition and concentration are shown to depend on O₃ concentration and dose, conditioning method, and adsorbent type and age. Calibrations showed good linearity, and most compounds had reasonable recoveries, for example, 90 ±15% for Tenax TA, 97 ±23% for Tenax GR, 101 ±24% for Carbopack B, and 79 ±25% (91 ±9% for n-aldehydes) for Carbopack X. Benzeneacetaldehyde recovery was notably poorer (22–63% across the four adsorbents). MDLs for several compounds were relatively high, up to 5 ng. By accounting for both artifact formation and method performance, this work helps to identify which carbonyl compounds can be measured using thermally desorbable adsorbents and which may be prone to bias because of the formation of O_3- adsorbent artifacts.