An Evaluation of the Semi-VOST Method for Determining Emissions from Hazardous Waste Incinerators

The Semi-Volatile Organic Sampling Train method was investigated to determine its reliability and to determine the bias and precision of the method when used to determine emissions from hazardous waste incinerators. Experiments showed that the matrix and sampling variables usually involved in sampling emissions from a hazardous waste incinerator had no significant effect on the recovery of 11 different organic compounds. Significant losses of the sampled compounds can occur during sample preparation. The degree of loss appears to be directly related to the compounds, vapor pressure. These losses can be corrected for by adding deuterated surrogates to the sample and analyzing the surrogates along with the native compounds.

The bias determination was based on dynamic spiking of the sampling train with five deuterated organic compounds selected from Appendix VIII of the Resource Conservation and Recovery Act regulations. The results show biases of from -1 ± 8 percent to -18 ± 27 percent for chlorinated and nonchlorinated compounds. Pyridine, a water-soluble compound, showed a larger bias of-29 ± 13 percent. Particular attention to the recovery of water soluble compounds is necessary to minimize bias in their determinations. Further work is needed to determine the reliability of laboratory-determined retention volumes that are used to determine sampling conditions.     

Use of Energy Scenarios in Addressing the CO2 Question

A reference scenario for CO₂ emissions was developed using a model of world energy supply and demand. In the reference scenario, world GNP and world energy demand increase at average rates of 2.1 percent per year and 1.5 percent per year, respectively during the period 1975-2100. The corresponding annual CO₂ emissions rise to a maximum of 16 gigatons of carbon around 2050 and then decline as a result of a transition to nonfossil fuel energy systems. A modified scenario for high CO₂ emissions was obtained by assuming an abundant supply of low cost coal, thus eliminating the transition. A low case was developed in which the low cost of alternative energy (i.e., solar, nuclear) induces an earlier shift away from fossil fuels.

Annual emissions of the three scenarios were used as input to a global carbon cycle model and the CO₂ buildup in the atmosphere during the period 1980-2100 was determined by the model. All three scenarios showed continuous rises in atmospheric CO₂ concentration. The reference scenario reached 775 ppm by 2100. The high CO₂ case resulted in concentrations of over 1040 ppm, and for the low case the 2100 concentration was just under 700 ppm. If the climate theory is correct, even 700 ppm is sufficient to give significant climate warming, but by experiencing the change gradually over a century, adaptation may not be painful. An early transition to nonfossil fuel supplies makes the problem less severe but does not eliminate it.     

A New Audit Technique for EPA Method 25

A simple, inexpensive, and accurate technique for evaluating or auditing the sampling, recovery, and analytical phases of EPA Source Reference Method 25 has been developed. The technique involves spiking a U-shaped stainless steel cartridge containing Tenax® with known quantities of selected organic compounds and thermally desorbing them at temperatures from 160°C to 180°C to generate organic vapors quantitatively. The major advantages of this technique are that no other measurement methods can be used to determine the generated organic concentrations in lieu of Method 25; and that the cartridge can easily be taken to the field for evaluation. The organic compounds generated in test runs are collected and analyzed using the Method 25 procedure. The generation of organics is quantitative and recoveries were found to be 100 ± 10%. The time required for desorption of the majority of organics is generally less than forty-five minutes at a flow rate of 100 mL/min; however, based on laboratory experience the recommended sampling time is sixty minutes. These spiked cartridges are stable at room temperature over a two-month period. Results of interlaboratory studies showed close agreement with the expected concentrations based on calculations from the mass loadings and sample volumes.     

Development of Federal Air Standards to Reduce Sulfur Dioxide Emissions from New Industrial Boilers

Federal new source performance standards to control air emissions of sulfur dioxide from new industrial boilers were proposed by EPA on June 19, 1986. These standards would require boiler owners to reduce SO₂ emissions by 90 percent and meet an emission limit of 1.2 lb/MM Btu of heat input for coal-fired boilers and 0.8 lb/MM Btu for oil-fired boilers. In developing these standards, several regulatory options were considered, from standards that could be met by firing low sulfur fuels to standards that would necessitate flue gas treatment. The environmental, economic, and cost impacts of each option were analyzed. National impacts were estimated by a computer model that projects the population of new boilers over the 5-year period following proposal, predicts the compliance strategy that will be used to comply with the particular option (always assuming that the lowest cost method of compliance will be selected), and estimates the resulting emission reductions and costs. Impacts on specific industries and on model boilers were also analyzed. This paper focuses on these analyses and their results. The Agency's conclusions from these analyses, which led to the decision to establish percent reduction standards, are provided, and the proposed SO₂ standards are summarized. The proposed standards also include an emission limit for particulate matter from oil-fired boilers (0.1 lb/MM Btu). However, this article focuses only on the SO₂ standards.     

An Assessment of the Economic Effects of Ozone on U.S. Agriculture

Past attempts to measure the economic consequences of ozone on agriculture have been based on limited plant science information. This paper reports on an economic assessment of ozone on U.S. agriculture using recent crop response data from the National Crop Loss Assessment Network (NCLAN). The results are derived from a U.S. agricultural sector model that includes major crop and livestock production as well as domestic consumption, livestock feeding and export uses. The economic effects of four hypothetical ambient ozone levels are investigated. The analysis Indicates that the benefits to society of moderate (25%) ozone reductions are approximately $1.7 billion. A 25% Increase in ozone pollution results in costs (negative benefits) of $2.1 billion. These estimates do not reflect compliance costs of achieving the ozone changes and hence are not net benefits.     

Spatial distribution of ciguateric fish in the Republic of Kiribati

Ciguatera is food poisoning caused by human consumption of reef fish contaminated with ciguatoxins (CTXs). The expanding international trade of tropical fish species from ciguatera-endemic regions has resulted in increased global incidence of ciguatera, and more than 50 000 people are estimated to suffer from ciguatera each year worldwide. The Republic of Kiribati is located in the Pacific Ocean; two of its islands, Marakei and Tarawa, have been suggested as high-risk areas for ciguatera. The toxicities of coral reef fish collected from these islands, including herbivorous, omnivorous and carnivorous fish (24% [n = 41], 8% [n = 13] and 68% [n = 117], respectively), were analyzed using the mouse neuroblastoma assay (MNA) after CTX extraction. The MNA results indicated that 156 fish specimens, or 91% of the fish samples, were ciguatoxic (CTX levels >0.01 ng g⁻¹). Groupers and moray eels were generally more toxic by an order of magnitude than other fish species. All of the collected individuals of eight species (n = 3-19) were toxic. Toxicity varied within species and among locations by up to 10 000-fold. Cephalapholis argus and Gymnothorax spp. collected from Tarawa Island were significantly less toxic than those from Marakei Island, although all individuals were toxic based on the 0.01 ng g⁻¹ threshold. CTX concentrations in the livers of individuals of two moray eel species (Gymnothorax spp., n = 6) were nine times greater than those in muscle, and toxicity in liver and muscle showed a strong positive correlation with body weight. The present study provides quantitative information on the ciguatoxicity and distribution of toxicity in fish for use in fisheries management and public health.     

Polychlorinated dibenzo-p-dioxin and dibenzofuran in urban air of an Andean city

Particle-bound polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in ambient air were monitored together with particulate matter less than 10 μm (PM₁₀) at three sampling sites of the Andean city of Manizales, Colombia; during September 2009 and July 2010. PCDD/Fs ambient air emissions ranged from 1 fg WHO-TEQ m⁻³ to 52 fg WHO-TEQ m⁻³ in particulate fraction. The PM₁₀ concentrations ranged from 23 μg m⁻³ to 54 μg m⁻³. Concentrations of PM₁₀ and PCDD/Fs in ambient air observed for Manizales - a medium sized city with a population of 380 000 - were comparable to concentrations in larger cities. The highest concentrations of PCDD/Fs and PM₁₀ found in this study were determined at the central zone of the city, characterized by public transportation density, where diesel as principal fuel is used. In addition, hypothetical gas fractions of PCDD/Fs were calculated from theoretical K_p data. Congener profiles of PCDD/Fs exhibited ratios associated with different combustion sources at the different sampling locations, ranging from steel recycling to gasoline and diesel engines. Taking into account particle and gas hypothetical fraction of PCDD/Fs, Manizales exhibited values of PCDD/Fs equivalent to rural and urban-industrial sites in the southeast and center of the city respectively. Poor correlation of PCDDs with PM₁₀ (r = −0.55 and r = 0.52) suggests ambient air PCDDs were derived from various combustion sources. Stronger correlation was observed of PCDFs with PM₁₀. Poor correlation between precipitation and reduced PM₁₀ concentration in ambient air (r = −0.45) suggested low PM₁₀ removal by rainfall.     

Estimating contaminant mass discharge: a field comparison of the multilevel point measurement and the integral pumping investigation approaches and their uncertainties

In this field study, two approaches to assess contaminant mass discharge were compared: the sampling of multilevel wells (MLS) and the integral groundwater investigation (or integral pumping test, IPT) that makes use of the concentration-time series obtained from pumping wells. The MLS approached used concentrations, hydraulic conductivity and gradient rather than direct chemical flux measurements, while the IPT made use of a simplified analytical inversion. The two approaches were applied at a control plane located approximately 40m downgradient of a gasoline source at Canadian Forces Base Borden, Ontario, Canada. The methods yielded similar estimates of the mass discharging across the control plane. The sources of uncertainties in the mass discharge in each approach were evaluated, including the uncertainties inherent in the underlying assumptions and procedures. The maximum uncertainty of the MLS method was about 67%, and about 28% for the IPT method in this specific field situation. For the MLS method, the largest relative uncertainty (62%) was attributed to the limited sampling density (0.63 points/m(2)), through a novel comparison with a denser sampling grid nearby. A five-fold increase of the sampling grid density would have been required to reduce the overall relative uncertainty for the MLS method to about the same level as that for the IPT method. Uncertainty in the complete coverage of the control plane provided the largest relative uncertainty (37%) in the IPT method. While MLS or IPT methods to assess contaminant mass discharge are attractive assessment tools, the large relative uncertainty in either method found for this reasonable well monitored and simple aquifer suggests that results in more complex plumes in more heterogeneous aquifers should be viewed with caution.     

Cobalt-induced oxidative stress in brain, liver and kidney of goldfish Carassius auratus

Cobalt is an essential element, but at high concentrations it is toxic. In addition to its well-known function as an integral part of cobalamin (vitamin B₁₂), cobalt has recently been shown to be a mimetic of hypoxia and a stimulator of the production of reactive oxygen species. The present study investigated the responses of goldfish, Carassius auratus, to 96 h exposure to 50, 100 or 150 mg L⁻¹ Co²⁺ in aquarium water (administered as CoCl₂). The concentrations of cobalt in aquaria did not change during fish exposure. Exposure to cobalt resulted in increased levels of lipid peroxides in brain (a 111% increase after exposure to 150 mg L⁻¹ Co²⁺) and liver (30-66% increases after exposure to 50-150 mg L⁻¹ Co²⁺), whereas the content of protein carbonyls rose only in kidney (by 112%) after exposure to 150 mg L⁻¹ cobalt. Low molecular mass thiols were depleted by 24-41% in brain in response to cobalt treatment. The activities of primary antioxidant enzymes, superoxide dismutase (SOD) and catalase, were substantially suppressed in brain and liver as a result of Co²⁺ exposure, whereas in kidney catalase activity was unchanged and SOD activity increased. The activities of glutathione-related enzymes, glutathione peroxidase and glutathione-S-transferase, did not change as a result of cobalt exposure, but glutathione reductase activity increased by ∼40% and ∼70% in brain and kidney, respectively. Taken together, these data show that exposure of fish to Co²⁺ ions results in the development of oxidative stress and the activation of defense systems in different goldfish tissues.     

Ecotoxicity evaluation of selected sulfonamides

Sulfonamides (SAs) are a group of antibiotic drugs widely used in veterinary medicine. The contamination of the environment by these pharmaceuticals has raised concern in recent years. However, knowledge of their (eco)toxicity is still very basic and is restricted to just a few of these substances. Even though their toxicological analysis has been thoroughly performed and ecotoxicological data are available in the literature, a systematic analysis of their ecotoxicological potential has yet to be carried out. To fill this gap, 12 different SAs were chosen for detailed analysis with the focus on different bacteria as well as non-target organisms (algae and plants). A flexible (eco)toxicological test battery was used, including enzymes (acetylcholinesterase and glutathione reductase), luminescent marine bacteria (Vibrio fischeri), soil bacteria (Arthrobacter globiformis), limnic unicellular green algae (Scenedesmus vacuolatus) and duckweed (Lemna minor), in order to take into account both the aquatic and terrestrial compartments of the environment, as well as different trophic levels. It was found that SAs are not only toxic towards green algae (EC₅₀ = 1.54-32.25 mg L⁻¹) but have even stronger adverse effect on duckweed (EC₅₀ = 0.02-4.89 mg L⁻¹) than atrazine - herbicide (EC₅₀ = 2.59 mg L⁻¹).