Refinery evaluation of optical imaging to locate fugitive emissions

Fugitive emissions account for approximately 50% of total hydrocarbon emissions from process plants. Federal and state regulations aiming at controlling these emissions require refineries and petrochemical plants in the United States to implement a Leak Detection and Repair Program (LDAR). The current regulatory work practice, U.S. Environment Protection Agency Method 21, requires designated components to be monitored individually at regular intervals. The annual costs of these LDAR programs in a typical refinery can exceed US$1,000,000. Previous studies have shown that a majority of controllable fugitive emissions come from a very small fraction of components. The Smart LDAR program aims to find cost-effective methods to monitor and reduce emissions from these large leakers. Optical gas imaging has been identified as one such technology that can help achieve this objective. This paper discusses a refinery evaluation of an instrument based on backscatter absorption gas imaging technology. This portable camera allows an operator to scan components more quickly and image gas leaks in real time. During the evaluation, the instrument was able to identify leaking components that were the source of 97% of the total mass emissions from leaks detected. More than 27,000 components were monitored. This was achieved in far less time than it would have taken using Method 21. In addition, the instrument was able to find leaks from components that are not required to be monitored by the current LDAR regulations. The technology principles and the parameters that affect instrument performance are also discussed in the paper.     

International trade in meat: the tip of the pork chop

This paper provides an original account of global land, water, and nitrogen use in support of industrialized livestock production and trade, with emphasis on two of the fastest-growing sectors, pork and poultry. Our analysis focuses on trade in feed and animal products, using a new model that calculates the amount of "virtual" nitrogen, water, and land used in production but not embedded in the product. We show how key meat-importing countries, such as Japan, benefit from "virtual" trade in land, water, and nitrogen, and how key meat-exporting countries, such as Brazil, provide these resources without accounting for their true environmental cost. Results show that Japan's pig and chicken meat imports embody the virtual equivalent of 50% of Japan's total arable land, and half of Japan's virtual nitrogen total is lost in the US. Trade links with China are responsible for 15% of the virtual nitrogen left behind in Brazil due to feed and meat exports, and 20% of Brazil's area is used to grow soybean exports. The complexity of trade in meat, feed, water, and nitrogen is illustrated by the dual roles of the US and The Netherlands as both importers and exporters of meat. Mitigation of environmental damage from industrialized livestock production and trade depends on a combination of direct-pricing strategies, regulatory approaches, and use of best management practices. Our analysis indicates that increased water- and nitrogen-use efficiency and land conservation resulting from these measures could significantly reduce resource costs.     

Taboos and forest governance: informal protection of hot spot dry forest in southern Madagascar

In the dry forest of southern Madagascar, a region of global conservation priority, formally protected areas are nearly totally absent. We illustrate how the continued existence of unique forest habitats in the Androy region is directly dependent on informal institutions, taboos, regulating human behavior. Qualitative interviews to map and analyze the social mechanisms underlying forest protection have been combined with vegetation analyses of species diversity and composition. Of 188 forest patches, 93% were classified as protected, and in Southern Androy all remaining forest patches larger than 5 ha were protected. Eight different types of forests, with a gradient of social fencing from open access to almost complete entry prohibitions, were identified. Transgressions were well enforced with strong sanctions of significant economic as well as religious importance. Analyses of species diversity between protected and unprotected forests were complicated because of size differences and access restrictions. However, since, for example, in southern Androy >90% of the total remaining forest cover is protected through taboos, these informal institutions represent an important, and presently the only, mechanism for conservation of the highly endemic forest species. We conclude that social aspects, such as local beliefs and legitimate sanctioning systems, need to be analyzed and incorporated along with biodiversity studies for successful conservation.     

Management options and effects on a marine ecosystem: assessing the future of the Baltic

We are using the coupled models in a decision support system, Nest, to evaluate the response of the marine ecosystem to changes in external loads through various management options. The models address all the seven major marine basins and the entire drainage basin of the Baltic Sea. A series of future scenarios have been developed, in close collaboration with the Helsinki Commission, to see the possible effects of improved wastewater treatment and manure handling, phosphorus-free detergents, and less intensive land use and live stocks. Improved wastewater treatment and the use of phosphorus-free detergents in the entire region would drastically decrease phosphorus loads and improve the marine environment, particularly the occurrence of cyanobacterial blooms. However, the Baltic Sea will remain eutrophic, and to reduce other effects, a substantial reduction of nitrogen emissions must be implemented. This can only be obtained in these scenarios by drastically changing land use. In a final scenario, we have turned 50% of all agricultural lands into grasslands, together with efficient wastewater treatments and a ban of phosphorus in detergents. This scenario will substantially reduce primary production and the extension of hypoxic bottoms, increase water transparency in the most eutrophied basins, and virtually eliminate extensive cyanobacterial blooms.     

Determination of selenium by GFAAS in slurries of fish feces to estimate the bioavailability of this micronutrient in feed used in pisciculture

This paper presents a simple, fast and sensitive method to determine selenium in samples of feces and of fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of selenium) were 0.31 microg l(-1) and 1.03 microg l(-1), respectively, for the standard feces slurries and 0.35 microg l(-1) and 1.16 microg l(-1), respectively, for the standard feed slurries. The proposed method was applied in studies of bioavailability of selenium in different fish feeds and the results proved consistent with that obtained from samples mineralized by acid digestion using the microwave oven.     

Development and verification of a toxicokinetic model of polychlorinated biphenyl elimination in persons working in a contaminated building

BACKGROUND: Polychlorinated biphenyls are toxic and slowly degrading substances that have been in widespread industrial use in the 1960s and 1970s. Despite a worldwide reduction, environmental exposure remains an issue; the assessment of an individual's level of exposure at a given time in retrospect requires valid toxicokinetic modeling of the different PCB congeners. OBJECTIVES: To develop and verify a toxicokinetic model of the in vivo-degradation of PCB 28 and 52 in adult humans. METHODS: The plasma concentrations of PCB congeners were measured in 583 persons working in a contaminated building for an average of 14.7+/-9.6 years. The values were adapted to a simple pharmacokinetic model (yt = y0 x (1 - e(-kt))); the steady state concentration y0 was estimated based on the median values of persons working exposed more than 10 years. RESULTS: The steady state concentration of PCB 28 was 0.10 microg/l, that of PCB 52 0.02 microg/l. The half-life of the congeners was estimated based on a logarithmic regression analysis according to the model mentioned above; it was 2.18 (95% CI: 1.91-2.54) years for PCB 28 and 3.95 (95% CI: 3.55-4.45) years for PCB 52, respectively. Stepwise elimination of persons with very long employment duration did not reduce the estimated half-life. CONCLUSIONS: The estimated half-life is higher than previously published data especially for PCB 52. Possible reasons and implications of this finding are discussed.     

Fluorescence fingerprints and Cu2+-complexing ability of individual molecular size fractions in soil- and waste-borne DOM

Land spreading of organic materials introduces large amounts of dissolved organic matter (DOM) into the soil. DOM has the ability to form stable complexes with heavy metals and can facilitate their transport towards the groundwater. The effects on soil processes are difficult to assess, because different DOM components might react differently towards metal ions. The objective of this study was to investigate the fluorescence signature and the Cu2+-binding capacity of individual molecular size fractions of DOM from various sources. DOM extracted from leaf compost, chicken manure, sugar cane vinasse and a fulvic hypercalcaric cambisol was fractionated by the means of dialysis into four molecular size classes: MW<500, 50012000-14000 Da. Vinasse and leaf compost contained around 80% and 70%, respectively, of the total organic carbon in the fractions with low molecular weight (MW<3500 Da); in chicken manure and soil these fractions accounted for 40% and 50% only. Fluorescence was highest in the fraction MW>12000 Da for leaf compost, chicken manure and soil. The opposite result was obtained for vinasse, where the fractions with low molecular weight showed highest fluorescence intensities, distinguishing it from all other samples. Vinasse showed the greatest ability to bind Cu2+ with a resulting complex concentration of 6.31mgl(-1) while in contact with an excess of Cu2+. Leaf compost, soil and chicken manure followed with 2.69, 1.12, and 0.85mgl(-1), respectively. Within vinasse, the fraction MW<500 Da was able to form the most DOM-Cu complexes, indicating the importance of low molecular weight fractions in metal binding.     

Kinetic and adsorption study of acid dye removal using activated carbon

The adsorption of three acid dyes, Acid Red 97, Acid Orange 61 and Acid Brown 425 onto activated carbon was studied for the removal of acid dyes from aqueous solutions at room temperature (25 degrees C). The adsorption of each dye with respect to contact time was then measured to provide information about the adsorption characteristics of activated carbon. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The experimental isotherms obtained, except for Acid Orange 61 studied in mixture, were of the S-type in terms of the classification of Giles and co-workers. The best fit of the adsorption isotherm data was obtained using the Freundlich model. When a comparative study was made of the results obtained with single and mixed dyes, it can be seen that some of them affect others and modify their behavior in the adsorption process. The results indicate that activated carbon could be employed for the removal of dyes from wastewater.     

Acetylcholinesterase-polyaniline biosensor investigation of organophosphate pesticides in selected organic solvents

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved.