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.     

Acid Rain in Downtown São Paulo City, Brazil

During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown São Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, $ \rm NH^{ + }_{4} During the period from July 2002 to June 2004, the chemical characteristics of the rainwater samples collected in downtown S?o Paulo were investigated. The analysis of 224 wet-only precipitation samples included pH and electrical conductivity, as well as major ions (Na⁺, , K⁺, Ca²⁺, Mg²⁺, Cl⁻, , ) and carboxylic acids (acetic, formic and oxalic) using ion chromatography. The volume weighted mean, VWM, of the anions , and Cl⁻ was, respectively, 20.3, 12.1 and 10.7 μmol l⁻¹. Rainwater in S?o Paulo was acidic, with 55% of the samples exhibiting a pH below 5.6. The VWM of the free H⁺ was 6.27 μmol l⁻¹), corresponding to a pH of 5.20. Ammonia (NH₃), determined as (VWM = 32.8 μmol l⁻¹), was the main acidity neutralizing agent. Considering that the H⁺ ion is the only counter ion produced from the non-sea-salt fraction of the dissociated anions, the contribution of each anion to the free acidity potential has the following profile: (31.1%), (26.0%), CH₃COO⁻ (22.0%), Cl⁻ (13.7%), HCOO⁻ (5.4%) and (1.8%). The precipitation chemistry showed seasonal differences, with higher concentrations of ammonium and calcium during autumn and winter (dry period). The marine contribution was not significant, while the direct vehicular emission showed to be relevant in the ionic composition of precipitation.     

Closed cycle construction: an integrated process for the separation and reuse of C&D waste

In The Netherlands, construction and demolition (C&D) waste is already to a large extent being reused, especially the stony fraction, which is crushed and reused as a road base material. In order to increase the percentage of reuse of the total C&D waste flow to even higher levels, a new concept has been developed. In this concept, called 'Closed Cycle Construction', the processed materials are being reused at a higher quality level and the quantity of waste that has to be disposed of is minimised. For concrete and masonry, the new concept implies that the material cycle will be completely closed, and the original constituents (clay bricks, gravel, sand, cement stone) are recovered in thermal processes. The mixed C&D waste streams are separated and decontaminated. For this purpose several dry separation techniques are being developed. The quality of the stony fraction is improved so much, that this fraction can be reused as an aggregate in concrete. The new concept has several benefits from a sustainability point of view, namely less energy consumption, less carbon dioxide emission, less waste production and less land use (for excavation and disposal sites). One of the most remarkable benefits of the new concept is that the thermal process steps are fuelled with the combustible fraction of the C&D waste itself. Economically the new process is more or less comparable with the current way of processing C&D waste. On the basis of the positive results of a feasibility study, currently a pilot and demonstration project is being carried out. The aim is to optimise the different process steps of the Closed Cycle Construction process on a laboratory scale, and then to verify them on a large scale. The results of the project are promising, so far.     

Reusing fly ash in glass fibre reinforced cement: a new generation of high-quality GRC composites

New composite materials based on an alkali-resistant glass-fibre reinforced cement (AR-GRC) system are being developed by using fly ash (FA) produced at coal thermoelectric power plants, and fluid catalytic cracking catalyst residue (FC3R) from the petrol industry as cement replacement materials. These wastes are reactive from the pozzolanic viewpoint, and modify the nature and the microstructure of the cement matrix when a part of the Portland cement is replaced in the formulation of GRC. Several microstructural and mechanical aspects are being studied for AR-GRC systems. The behaviour of composites exposed to ageing shows that the pozzolanic activity of the ground FA added in high amounts and its mixture with the FC3R increase the flexural strength and no evidences of strength decay are observed. Additionally, the fibres due to the high alkalinity of the cementing matrix can be deteriorated. Fibres in the control (only Portland cement) and FC3R containing composites were attacked, whereas composites with FA and their mixture with FC3R show that the fibres have not been attacked, due to the pozzolanic activity of replacing materials that reduce the calcium hydroxide content in the cementing matrix.     

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.     

Variations in PCB concentrations between genders of six warmwater fish species in Lake Logan Martin, Alabama, USA

We collected and analyzed 955 individual fish (six species) for sexual differences in PCB bioaccumulations from a southeastern, USA reservoir. Using 2-way ANCOVAs, we found significant differences in fillet PCB concentrations between sexes for channel catfish (Ictalurus punctatus), largemouth bass (Micropterus salmoides) and spotted bass (Micropterus punctulatus). Striped bass (Morone saxatilus), black crappie (Pomoxis nigromaculatus) and freshwater drum (Aplodinotus grunniens) did not display differences between sexes in PCB concentrations. We suspect that sexual differences may be due to biological differences in reproduction, relative motility and lipid deposition. For one species (striped bass), sexual differences in PCB concentrations were inconsistent with a study in the Hudson River suggesting that sexual differences in bioaccumulations can change across ecosystems. Two species which did show sexual differences, largemouth bass and channel catfish, are often chosen as representative species (e.g., "piscivore" and "benthivore") in contaminant monitoring in many USA states indicating human consumption and risk management decisions would be improved if an equal number of male and female fish were included in composite PCBs analysis. This could reduce variability in fish PCBs data from which consumption advisories are based.     

Multiresidue analysis of pesticides in fruits and vegetables by gas chromatography-mass spectrometry

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids, triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extraction (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3 mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products for routine monitoring programs.     

A two-generational reproductive toxicity study of zinc in rats

A two-generation reproductive toxicity study of zinc chloride (ZnCl(2)) was conducted in rats. F(o) male and female rats were administered 0.00 (control), 7.50 (low), 15.00 (mid) and 30.00 (high) mg/kg/day of ZnCl(2). Selected F(1) male and female rats were exposed to the same doses received by their parents (F(o)). Exposure of F(0) parental rats to ZnCl(2) showed significant reduction in fertility, viability (days 0 and 4), and the body weight of F(1) pups from the high-dose group but caused no effects on litter size, weaning index, and sex ratio. Similarly, the continued exposure of F(1) parental rats to ZnCl(2) also reduced fertility, liter size, viability (day 0), and the body weight of F(2) pups within the high-dose group but caused no effects on weaning index and sex ratio. Exposure of ZnCl(2) to F(0) and F(1) parental males resulted in a significant reduction in their body weights, and the F(0) and F(1) parental females did not show any significant difference in their body weights compared to their control groups. However, the postpartum dam weights of both F(0) and F(1) female rats were significantly reduced compared to their controls. Exposure of ZnCl(2) to F(o) and F(1) generation parental rats did not produce any significant change of their clinical signs as well as their clinical pathology parameters, except the alkaline phosphotase (ALK) level, which showed an upward trend in both sexes of both generations. Exposure of ZnCl(2) to F(0) rats resulted in a reduction of brain, liver, kidney, spleen and seminal vesicles weights of males and in the spleen and uterus of females. Similarly, exposure of F(1) rats to ZnCl(2) also resulted in reduction of brain, liver, kidney, adrenal, spleen, prostate and seminal vesicles weights of males and in spleen and uterus of females. ZnCl(2) exposure resulted in grossly observed gastro-intestianla (GI) tract, lymphoreticular/hematopoietic, and reproductive tract lesions in parental rats in both generations. Reduced body fat was also recorded in F(1) parental rats.     

Uptake and accumulation of cadmium, lead and zinc by Siam weed [Chromolaena odorata (L.) King & Robinson

The Siam weed, Chromolaena odorata (L.) King & Robinson, Family Asteraceae, was found to be a new Pb hyperaccumulator by means of field surveys on Pb soil and hydroponic studies. Plants from field collection accumulated 1377 and 4236mgkg(-1) Pb in their shoots and roots, respectively, and could tolerate soil Pb concentrations up to 100000 mgkg(-1) with a translocation factor of 7.62. Very low concentrations of Cd and Zn were found in plants collected from the field. Under nutrient solution culture condition, C. odorata from the contaminated site (CS) and from non-contaminated site (NCS) grew normally with all three metals (Pb, Cd, Zn) supplied. However, the relative growth rates of all treated plants decreased with increased metal concentrations. The percentage uptakes of Pb, Cd, and Zn by C. odorata increased with increasing metal concentrations. Pb concentration in shoots and roots reached its highest values (1772.3 and 60655.7mgkg(-1), respectively) at a Pb supply level of 10mgl(-1). While the maximum concentrations of Cd (0.5mgl(-1)) in shoots and roots of C. odorata were 102.3 and 1440.9mgkg(-1), and the highest concentrations of Zn (20mgl(-1)) were 1876.0 and 7011.8mgkg(-1), respectively. The bioaccumulation coefficients of Pb and Cd were greater than 1000. These results confirm that C. odorata is a hyperaccumulator which grows rapidly, has substantial biomass, wide distribution and has a potential for the phytoremediation of metal contaminated soils.     

Structure of Mn-Zr mixed oxides catalysts and their catalytic performance in the gas-phase oxidation of chlorocarbons

The catalytic activity and selectivity of manganese zirconia mixed oxides were evaluated for the oxidation of two common chlorinated pollutants found in waste streams, namely 1,2-dichloroethane (DCE) and trichloroethylene (TCE). Mixed oxides with varying Mn-Zr content were prepared by coprecipitation via nitrates, and subsequent calcination at 600 degrees C for 4 h in air. These catalysts were characterised by means of several techniques such as atomic emission spectrometry, N2 adsorption-desorption, powder X-ray diffraction, temperature-programmed desorption of ammonia, pyridine adsorption followed by diffuse reflectance infrared spectroscopy and temperature-programmed reduction with hydrogen. The active catalytic behaviour of Mn-Zr mixed oxides was ascribed to a substantial surface acidity combined with readily accessible active oxygen species. Hence, the mixed oxide with 40 mol% manganese content was found to be an optimum catalyst for the combustion of both chlorocarbons with a T50 value around 305 and 315 degrees C for DCE and TCE oxidation, respectively. The major oxidation products were carbon dioxide, hydrogen chloride and chlorine. It was observed that the formation of both CO2 and Cl2 was promoted with Mn loading.