Flow Injection Analysis of MWC Fly Ash Leaching Characteristics

Abstract

A completely mixed batch reactor leaching method utilizing flow injection analysis (the CMBR-FIA method) was developed to study the lead leaching characteristics of municipal waste combustor fly ash. Flow injection analysis (FIA) coupled with atomic absorption spectrophotometry enabled the determination of lead concentrations at one minute intervals. The pH and oxidation-reduction potential of the solution were continuously monitored to characterize the leaching conditions. Automatic titration was used to alter the solution pH to defined endpoints. The CMBR-FIA method offers the ability to immediately observe alterations to the leaching solution, and grants the freedom to study a number of parameters concurrently. The CMBR-FIA method is a rapid and reliable means to investigate leaching characteristics. This paper describes the method and demonstrates its use to monitor the leaching of lead from municipal solid waste combustor fly ash as a function of pH. Soluble lead concentrations are shown to increase quickly with decreasing pH.

A maximum of 50% of the total lead concentration was available in solution at pH 2. This value gradually decreased with time to over 35% of the total.     

Variables affecting emissions of PCDD/Fs from uncontrolled combustion of household waste in barrels

The uncontrolled burning of household waste in barrels has recently been implicated as a major source of airborne emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs). A detailed, systematic study to understand the variables affecting emissions of PCDD/Fs from burn barrels was performed. The waste composition, fullness of the barrel, and the combustion conditions within the barrel all contribute significantly to determining the emissions of PCDD/Fs from burn barrels. The study found no statistically significant effect on emissions from the Cl content of waste except at high levels, which are not representative of typical household waste. At these elevated Cl concentrations, the impact of Cl on PCDD/F emissions was found to be independent of the form of the Cl (inorganic or organic). For typical burn conditions, most of the PCDD/F emissions appear to be associated with the later stages of the burn when the waste is smoldering. Polychlorinated biphenyls (PCBs) were also measured for a subset of the tests. For the nominal waste composition, the average emissions were 76.8 ng toxic equivalency units (TEQ)WHO98/kg of waste combusted, which suggests that uncontrolled burning of household waste could be a major source of airborne PCDD/Fs in the United States.     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

Archaeometric researches on the provenance of Mediterranean Archaic Phoenician and Punic pottery

The aim of this study is to setup a first chemical database that could represent the starting point for a reliable classification method to discriminate between Archaic Phoenician and Punic pottery on the base of their chemical data. This database up to now can discriminate between several different areas of production and provenance and can be applied also to unknown ceramic samples of comparable age and production areas. More than 100 ceramic fragments were involved in this research, coming from various archaeological sites having a crucial importance in the context of the Phoenician and Punic settlement in central and western Mediterranean: Carthage (Tunisia), Toscanos (South Andalusia, Spain), Sulci, Monte Sirai, Othoca, Tharros (Sardinia, Italy) and Pithecusa (Campania, Italy). Since long-time archaeologists hypothesised that Mediterranean Archaic Phoenician and Punic pottery had mainly a local or just a regional diffusion, with the exception of some particular class like transport amphorae. To verify the pottery provenance, statistical analyses were carried out to define the existence of different ceramic compositional groups characterised by a local origin or imported from other sites. The existing literature data are now supplemented by new archaeometric investigations both on Archaic Phoenician ceramics and clayey raw materials from Sardinia. Therefore, diffractometric analyses, optical microscopy observations and X-ray fluorescence analyses were performed to identify the mineralogical and chemical composition of Othoca ceramics and clayey raw material. The obtained results were then compared with own literature data concerning Phoenician and Punic pottery in order to find features related to the different ceramic productions and their provenance. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were also performed on the chemical compositional data in order to discriminate ceramic groups. A very complex situation was found: imported ceramics coming from Carthage, with a large-scale distribution, were found together with a predominant local production pottery. The archaeometric results demonstrate that historical and typological approach has to be supported by scientific analyses to better understand local or Mediterranean exchanges.     

Analysis and comparison of inertinite-derived adsorbent with conventional adsorbents

To increase U.S. petroleum energy-independence, the University of Texas at Arlington (UT Arlington) has developed a coal liquefaction process that uses a hydrogenated solvent and a proprietary catalyst to convert lignite coal to crude oil. This paper reports on part of the environmental evaluation of the liquefaction process: the evaluation of the solid residual from liquefying the coal, called inertinite, as a potential adsorbent for air and water purification. Inertinite samples derived from Arkansas and Texas lignite coals were used as test samples. In the activated carbon creation process, inertinite samples were heated in a tube furnace (Lindberg, Type 55035, Arlington, UT) at temperatures ranging between 300 and 850 degrees C for time spans of 60, 90, and 120 min, using steam and carbon dioxide as oxidizing gases. Activated inertinite samples were then characterized by ultra-high-purity nitrogen adsorption isotherms at 77 K using a high-speed surface area and pore size analyzer (Quantachrome, Nova 2200e, Kingsville, TX). Surface area and total pore volume were determined using the Brunauer Emmet, and Teller method, for the inertinite samples, as well as for four commercially available activated carbons (gas-phase adsorbents Calgon Fluepac-B and BPL 4 x 6; liquid-phase adsorbents Filtrasorb 200 and Carbsorb 30). In addition, adsorption isotherms were developed for inertinite and the two commercially available gas-phase carbons, using methyl ethyl ketone (MEK) as an example compound. Adsorption capacity was measured gravimetrically with a symmetric vapor sorption analyzer (VTI, Inc., Model SGA-100, Kingsville, TX). Also, liquid-phase adsorption experiments were conducted using methyl orange as an example organic compound. The study showed that using inertinite from coal can be beneficially reused as an adsorbent for air or water pollution control, although its surface area and adsorption capacity are not as high as those for commercially available activated carbons. Implications: The United States currently imports two-thirds of its crude oil, leaving its transportation system especially vulnerable to disruptions in international crude supplies. UT Arlington has developed a liquefaction process that converts coal, abundant in the United States, to crude oil. This work demonstrated that the undissolvable solid coal residual from the liquefaction process, called inertinite, can be converted to an activated carbon adsorbent. Although its surface area and adsorption capacity are not as high as those for commercially available carbons, the inertinite source material would be available at no cost, and its beneficial reuse would avoid the need for disposal.     

Single-source impact analysis using three-dimensional air quality models

Isolating the effects of an individual emissions source on secondary air pollutants such as ozone and some components of particulate matter must incorporate complex nonlinear processes, be sensitive to small emissions perturbations, and account for impacts that may occur hundreds of kilometers away. The ability to evaluate these impacts is becoming increasingly important for efficient air quality management. Here, as part of a recent compliance enforcement action for a violation of the Clean Air Act and as an evaluation of ozone response to single-source emissions plumes, two three-dimensional regional photochemical air quality models are used to assess the impact on ozone from approximately 2000 to 3000 excess t/month of nitrogen oxides emitted from a single power plant in Ohio. Periods in May, July, and August are evaluated. Two sensitivity methods are applied: the "brute-force" (B-F) method and the decoupled direct method (DDM). Using DDM, maximum 1-hr averaged ozone concentrations are found to increase by up to 1.8, 1.3, and 2.2 ppbv during May, July, and August episodes, respectively, and concentration increases greater than 0.5 ppbv occur in Ohio, Pennsylvania, Maryland, New York, West Virginia, Virginia, and North and South Carolina. B-F results for the August episode show a maximum 1-hr averaged ozone concentration increase of 2.3 ppbv. Significant localized decreases are also simulated, with a maximum of 3.6 ppbv in Ohio during the August episode and decreases of 0.50 ppbv and greater in Ohio, Pennsylvania, Maryland, West Virginia, and Virginia. Maximum increases are compared with maximum decreases for the August period using second-order DDM and are found, in aggregate, to be greater in magnitude by 42%. When evaluated during hours when ozone concentrations exceed 0.060 ppm, the maximum increases in ozone are higher than decreases by 82%. The spatial extent of ozone increase in both cases is about triple that of reduction.     

Predator cues and an herbicide affect activity and emigration in an agrobiont wolf spider

Animals use chemical cues for signaling between species. However, anthropogenic chemicals might interrupt this natural chemical information flow, with potential impacts on predator-prey interactions. Our goal was to explore how Buccaneer® Plus, a common herbicide similar to Round-up® (active ingredient glyphosate), affected the interactions between intraguild predators. The wolf spider Pardosa milvina (Hentz, 1844) is numerically dominant in agricultural systems across the eastern United States, and often falls prey to or competes with the larger wolf spider, Hogna helluo (Walckenaer, 1837) and/or the carabid beetle, Scarites quadriceps (Chaudoir, 1843). We tested the effects of chemical cues from these intraguild predators and exposure to herbicide on the activity, emigration, and survival of P. milvina using a full-factorial laboratory experiment. Both predator cues and herbicide led to a decrease in movement by P. milvina. However, although H. helluo cues alone decreased movement, S. quadriceps cues only decreased movement when combined with herbicide. These results indicate that predation risk and herbicide application likely interact in complex ways to affect the movement of a major arthropod predator in agricultural systems, and thus may have complex effects on the food web.