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.     

Physical Properties, Photo- and Bio-degradation of Baked Foams Based on Cassava Starch, Sugarcane Bagasse Fibers and Montmorillonite

The objectives of this work were to develop biodegradable trays from cassava starch, sugarcane fibers and Na-montmorillonite (Na-MMT) using a baking process and to study the effects of these components on the physical properties, photo- and bio-degradation of the trays. The sample F20 (produced with 20 g fiber/100 g formulation) showed the maximum yield production (100 %). All formulations resulted in well-shaped trays with densities between 0.1941 and 0.2966 g/cm³. The addition of fibers and Na-MMT resulted in less dense and less rigid trays compared to control samples (only starch). The studied processing conditions resulted in good nanoclay dispersion, leading to the formation of an exfoliated structure. The evaluation of the photo-degradation stability of the trays under UV exposure for 336 h showed that a sample produced with a specific combination of fiber and nanoclay (20 g fiber and 5 g nanoclay/100 g formulation) had the highest loss in stress at break (91 %). Biodegradation assays showed that Control trays (starch) and F20 (20 g fiber/100 g formulation) lost a greater percentage of their weight after 90 days of incubation in soil, with losses of up to 85.50 and 82.70 %, respectively.     

Herbicide residues in grapes and wine

Abstract

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin ‐ persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small‐lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first‐order kinetics, within the period of “ first fermentation”; and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.     

Strontium isotope study of coal utilization by-products interacting with environmental waters

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.     

Volatile organic compounds in the unsaturated zone from radioactive wastes

Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0-2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m yr. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere.     

Effects of economic growth on biodiversity in the United States

For many citizens and policymakers, the empirical relationship between economic growth and biodiversity conservation has not been sufficiently established for purposes of identifying the types of economic policies amenable to biodiversity conservation. Some think economic growth conflicts with biodiversity conservation; others think economic growth conduces biodiversity conservation. With panel data from 1997‐2011, encompassing US continental states, we developed a series of statistical models to investigate the relationships among species endangerment, human population, and economic growth as indicated by GDP and per capita GDP. Species endangerment is highly correlated with population and GDP, and per capita GDP is a significant regressor of species endangerment. Across US continental states, competitive exclusion of non‐human species occurs via human economic growth and population growth.     

Nitrogen leaching from Douglas-fir forests after urea fertilization

Leaching of nitrogen (N) after forest fertilization has the potential to pollute ground and surface water. The purpose of this study was to quantify N leaching through the primary rooting zone of N-limited Douglas-fir [Pseudotsuga menziesii (Mirb.) Franco] forests the year after fertilization (224 kg N ha(-1) as urea) and to calculate changes in the N pools of the overstory trees, understory vegetation, and soil. At six sites on production forests in the Hood Canal watershed, Washington, tension lysimeters and estimates of the soil water flux were used to quantify the mobilization and leaching of NO(3)-N, NH(4)-N, and dissolved organic nitrogen below the observed rooting depth. Soil and vegetation samples were collected before fertilization and 1 and 6 mo after fertilization. In the year after fertilization, the total leaching beyond the primary rooting zone in excess of control plots was 4.2 kg N ha(-1) (p = 0.03), which was equal to 2% of the total N applied. The peak NO(3)-N concentration that leached beyond the rooting zone of fertilized plots was 0.2 mg NO(3)-N L(-1). Six months after fertilization, 26% of the applied N was accounted for in the overstory, and 27% was accounted for in the O+A horizon of the soil. The results of this study indicate that forest fertilization can lead to small N leaching fluxes out of the primary rooting zone during the first year after urea application.     

Nutrient dynamics and tree growth of silvopastoral systems: impact of poultry litter

Fertilizing pastures with poultry litter has led to an increased incidence of nutrient-saturated soils, particularly on highly fertilized, well drained soils. Applying litter to silvopastures, in which loblolly pine (Pinus taeda L.) and bahiagrass (Paspalum notatum) production are integrated, may be an ecologically desirable alternative for upland soils of the southeastern USA. Integrating subterranean clover (Trifolium subterraneum) into silvopastures may enhance nutrient retention potential. This study evaluated soil nutrient dynamics, loblolly pine nutrient composition, and loblolly pine growth of an annually fertilized silvopasture on a well drained soil in response to fertilizer type, litter application rate, and subterranean clover. Three fertilizer treatments were applied annually for 4 yr: (i) 5 Mg litter ha(-1) (5LIT), (ii) 10 Mg litter ha(-1) (10LIT), and (iii) an inorganic N, P, K pasture blend (INO). Litter stimulated loblolly pine growth, and neither litter treatment produced soil test P concentrations above runoff potential threshold ranges. However, both litter treatments led to accumulation of several nutrients (notably P) in upper soil horizons relative to INO and unfertilized control treatments. The 10LIT treatment may have increased N and P leaching potential. Subterranean clover kept more P sequestered in the upper soil horizon and conferred some growth benefits to loblolly pine. Thus, although these silvopasture systems had a relatively high capacity for nutrient use and retention at this site, litter should be applied less frequently than in this study to reduce environmental risks.     

Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Contaminant-induced irreversible changes in properties of the soil-vadose-aquifer zone: an overview

Most studies on contaminant interactions with the subsurface environment focus on contaminant transport, retention and persistence, and on potential remediation of polluted soils, vadose zones and aquifers. Changes in the soil-vadose-aquifer zone (SVAZ) matrix and properties, caused by human activities, are thus usually considered to be deviations from a normal geochemical environment, which will disappear by natural processes or by specific remediation procedures. However, contaminants may also cause, under specific conditions, irreversible changes in SVAZ properties. In this critical overview, we discuss a different aspect of contaminant-SVAZ interactions: irreversible changes in natural SVAZ properties as a result of anthropogenically-induced chemical contamination. We survey selected research results that illustrate various aspects of such phenomena, in soils, aquifers and the vadose zone. Grouping contaminants according to major and trace elements, we observe that major elements can irreversibly affect water transmission and other physical and chemical properties of the SVAZ, mainly in the liquid phase, while trace elements affect mostly the solid phase matrix.