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.     

The effects of landscape-level disturbance on the composition of Minnesota caddisfly (Insecta: Trichoptera) trophic functional groups: evidence for ecosystem homogenization

Over 300,000 caddisfly specimens representing 249 species were collected from nearly 250 sites throughout Minnesota during 2000 and 2001 to determine the effects of human disturbance on the composition of caddisfly trophic functional groups at the landscape level. Canonical correspondence analysis determined that stream width was the most important variable influencing functional group composition in regions of the state with relatively low disturbance, and that differences in the caddisfly fauna between sizes of streams generally followed trends predicted by the river continuum concept. In regions of the state with moderate disturbance, both stream width and the percentage of disturbed habitat upstream of a site were important variables influencing functional group composition. In highly disturbed regions, no variables corresponded to changes in the composition of caddisfly functional groups. Instead, ecosystems were homogeneous: fine-particle filtering collectors dominated in all sizes of streams. The observed aquatic ecosystem homogenization is attributed mostly to input of fine-particle organic and inorganic sediment from extensive agriculture.     

Seasonal and Inter-Annual Variations in Methyl Mercury Concentrations in Zooplankton from Boreal Lakes Impacted by Deforestation or Natural Forest Fires

We compared the effects of natural and anthropogenic watershed disturbances on methyl mercury (MeHg) concentration in bulk zooplankton from boreal Shield lakes. MeHg in zooplankton was monitored for three years in nine lakes impacted by deforestation, in nine lakes impacted by wildfire, and in twenty lakes with undisturbed catchments. Lakes were sampled during spring, mid- and late summer. MeHg in zooplankton showed a seasonal trend: concentrations were the lowest in spring, then peaked in mid-summer and decreased in late summer. Over the three study years, MeHg concentrations observed in mid-summer in zooplankton from forest harvested lakes were significantly higher than in reference and fire-impacted lakes, whereas differences between these two groups of lakes were not significant. The pattern of distribution of MeHg in zooplankton during the different seasons paralleled that of dissolved organic carbon (DOC), which is known as a vector of Hg from watershed soils to lake water. Besides DOC, MeHg in zooplankton also showed a positive significant correlation with epilimnetic temperature and sulfate concentrations. An inter-annual decreasing trend in MeHg was observed in zooplankton from reference and fire-impacted lakes. In forest harvested lakes, however, MeHg concentrations remained higher and nearly constant over three years following the impact. Overall these results indicate that the MeHg pulse observed in zooplankton following deforestation by harvesting is relatively long-lived, and may have repercussions to the accumulation of MeHg along the food chain. Therefore, potential effects of deforestation on the Hg contamination of fish should be taken into account in forest management practices.     

Preparation and evaluation of candidate certified reference materials (CRMs) for nutrients in seawater

Certified reference materials (CRMs) are an essential part of the quality assurance (QA) necessary for the reliable analytical measurement of nutrients in seawater. The CRMs currently available for these analyses are not matrix matched to marine samples. QUASIMEME routinely produces test materials for the nutrients in seawater and nutrients in estuarine water and low-salinity open water Laboratory Performance Studies (LPS) that are both homogeneous and stable. QUASIMEME, in conjunction with Eurofins Scientific, Denmark have produced two reference materials (RMs). The homogeneity testing and preliminary stability studies were carried out by QUASIMEME, and the results are presented in this article. Participants of the QUASIMEME LPS who demonstrated satisfactory long-term performance for the analysis of nutrients in seawater and nutrients in estuarine water and low-salinity open water were invited to take part in the certification exercise. Twenty laboratories returned data, a summary of which is also presented. The certification and long-term stability testing and additional data analysis were carried out by Eurofins Scientific, Denmark, and are outwith the scope of this article and not reported here. Eurofins Scientific, Denmark have marketed these RMs as part of their range of VKI Reference Materials (further information is available from eurofins@eurofins.dk).     

A near real-time system for continuously monitoring airborne subtilisin-type enzymes in the industrial atmosphere

We describe the development and validation of a portable system comprising an air sampler coupled to an automated flow injection analysis device. The system is able to monitor airborne concentrations of subtilisin-type enzymes in the workplace atmosphere on a continuous basis. Sampling is in two stages: using a sampling head that is designed to mimic human respiration at approx. 1 m s(-1) at a sampling rate of 600 l min(-1). In the second stage, the captured particles are deposited by impaction from the air stream onto the inner surface of a cyclone that is continuously washed with a jet of buffer solution. Deposited particles are then washed into a reservoir from which samples are taken every 5-6 min and injected automatically into a continuous flow injection analysis system. Proteolytic enzyme in the sample passes through a bioreactor maintained at about 40 degrees C. This contains a cellulose solid phase matrix on which is covalently immobilised Texas Red-labelled gelatin as substrate. The passing enzyme partially digests the substrate releasing fluorophore that is detected down stream in a flow cell coupled to a fluorimeter. The system is calibrated using enzyme standards and the intensity of the resulting peaks from the ex-air samples is converted to airborne concentrations using a mathematical model programmed into a PC. The system has a limit of detection of 4.8 ng m(-3) and a dynamic range of 5-60 ng m(-3). The within assay precision (RSD) is 6.3-9.6% over this range. The within batch precision is 20.3% at 20 ng m(-3) and the corresponding between batch value is 19.5%. The system has been run for periods up to 8 h in the laboratory and for up to 4 h at a factory site and the values obtained compared with time-averaged values obtained from a conventional Galley sampler and in-house analysis when reasonable agreement of the results was observed. The stability of the system over 21 days of continuous use with standards injected periodically was studied. Linearity was observed for all the standard plots throughout. At the end of 21 days, after a total exposure equivalent to 2395 ng ml(-1) of Savinase, the signal due to the 5.0 ng ml(-1) standard was still easily detectable.     

Poisoned plusiines: toxicity of milkweed latex and cardenolides to some generalist caterpillars

Summary. Larvae of Trichoplusia ni Hübner (Lepidoptera: Noctuidae) that ingested latex from Asclepias curassavica L. (Asclepiadaceae) often regurgitated and convulsed with spasms before becoming immobile and unresponsive. Some larvae required over a day to recover sufficiently to feed. Latices from four other plant species in three families were all deterrent, but none caused detectable poisoning. The toxicity of A. curassavica latex was evidently due to cardenolides because pure cardenolides had similar effects when ingested by T. ni. Other species of noctuid caterpillars (Rachiplusia ou Guenée, Anagrapha falcifera Kirby, and Autographa precationis Guenée) sometimes also suffered spasms and temporary immobility when fed A. curassavica latex. A more distantly related noctuid, Spodoptera ornithogalli, was deterred by the latex, but showed no overt physiological responses at the dosage tested. T. ni larvae failed to develop on intact leaves of A. curassavica, on leaves with latex canals deactivated by midrib severance, and on excised leaves. Similarly, larvae reared on excised A. syriaca L. leaves to the final instar died when transferred to A. curassavica leaves with either intact or severed midribs. The final instar larvae sometimes suffered from spasms and immobility even when confined on leaves with depressurized canal systems. Evidently, cardenolides stored outside the latex system suffice to poison larvae. We conclude that cardenolides in A. curassavica have potent physiological effects on some generalist caterpillars and that the presence of these compounds both inside and outside laticifers effectively protects the plant. Received 30 June 1999; accepted 18 October 1999     

Coalitionary mate guarding by male chimpanzees at Ngogo, Kibale National Park, Uganda

Cooperative mate guarding by males is unusual in mammals and birds, largely because fertilizations are non-shareable. Chimpanzees live in fission-fusion communities that have cores of philopatric males who cooperate in inter-group aggression and in defending access to the females in their community. Male contest mating competition is restrained within communities, but single high-ranking males sometimes try to mate guard estrous females. Data from an unusually large chimpanzee commmunity at Ngogo, Kibale National Park, Uganda, that contains more males than any previously studied community show new variation in chimpanzee mate-guarding behavior. Contrary to expectation given the large number of males, mate guarding was as common as, or more common than, at other sites, and males other than the alpha male guarded more often. More strikingly, pairs or trios of top-ranking males sometimes engaged in cooperative aggression to prevent estrous females from mating with other males, but tolerated each other's mating activities. Both single males and coalitions mostly guarded periovulatory females. Mate-guarding coalitions were previously unknown in chimpanzees. Coalitions occurred in large mating parties, seemingly because these often contained too many males for single males to maintain exclusive access to estrous females. Coalition members gained higher shares of copulations than they could have expected from solo mate guarding, and suffered lower per capita costs of guarding (as inferred from aggression rates). Two males who most often participated in coalitions formed two-male coalitions at about the point where the number of males present made it unlikely that either could get 50% or more of total copulations on his own, and formed trios when this value dropped below 33%. Kin selection could be a factor in cooperation among male chimpanzees, but coalition members were not necessarily close relatives and the apparent structure of payoffs fit that of mutualism. Furthermore, reliance of male chimpanzees on support from allies to maintain high rank could have led to trading of mating exclusivity for support against mating competitors. Received: 28 May 1997 / Accepted after revision: 16 May 1998