Using Wet-FGD systems for mercury removal

A plan to control mercury emissions to the atmosphere and to establish mercury emission limits has recently been elaborated by the European Commission, making it necessary to devise an efficient and cost effective mercury removal technology. Towards this end wet flue gas desulfurization units appear as a promising option for multi-pollutant control. However, more investigation on mercury removal and a greater mercury removal efficiency are required to achieve this objective. In the present work scrubber chemistry and the application of various solid additives to enhance mercury removal in wet scrubbers is evaluated. The results obtained show a significant correlation between mercury removal efficiency and the pH of the scrubber slurry and SO2 concentration. A weaker correlation was observed between oxygen or slurry concentration and removal efficiency. Finally several solid oxides were found to be effective additives for enhancing mercury capture in wet scrubbers.     

Interlaboratory evaluation of endotoxin analyses in agricultural dusts--comparison of LAL assay and mass spectrometry

Endotoxin exposure is associated with wheeze and asthma morbidity, while early life exposure may reduce risk of allergy and asthma. Unfortunately, it is difficult to compare endotoxin results from different laboratories and environments. We undertook this study to determine if lipopolysaccharide (LPS) extraction efficiency could account for differences among laboratories. We generated and collected aerosols from chicken and swine barns, and corn processing. We randomly allocated side-by-side filter samples to five laboratories for Limulus assay of endotoxin. Lyophilized aliquots of filter extracts were analyzed for 3-hydroxy fatty acids (3-OHFAs) as a marker of LPS using gas chromatography-mass spectrometry. There were significant differences in endotoxin assay and GC-MS (LPS) results between laboratories for all dust types (p < 0.01). Patterns of differences between labs varied by dust type. Relationships between assay and GC/MS results also depended on dust type. The percentages of individual 3-OHFA chain lengths varied across labs (p < 0.0001) suggesting that each lab recovered a different fraction of the LPS available. The presence of large amounts of particle associated LPS and absence of a freezing thawing cycle were associated with lower correlations between LPS and bioactivity, consistent with an absence of Limulus response to cell-bound endotoxin. These data suggest that extraction methods affect endotoxin measurements. The LAL methods may be most suitable when comparing exposures within similar environments; GC-MS offers additional information helpful in optimizing sample treatment and extraction. GC-MS may be of use when comparing across heterogeneous environments and should be considered for inclusion in future studies of human health outcomes.     

Forest Area in Costa Rica: A Comparative Study of Tropical Forest Cover Estimates over Time

Forest area figures, at a given point in time and for a given region of interest, differ considerably, affecting the calculation of deforestation rates and thus confuse the political and scientific discussion on the state and change of the resource forest. This article discusses the variation of published forest cover figures, using Costa Rica as an example. A list of published figures on the forest cover of Costa Rica from 1940 onwards is analyzed. Reasons for the differences are hypothesized and discussed. These differences are mainly in the definition of forest and forest classes included, in the type of the studies conducted (mapping and/or sampling), in the precision of the estimates, and in the information sources used. It is concluded that part of the problem is inherent in the nature of the resource `forest'. Quality and completeness of the presentation of the forest cover estimates are a clue to their correct understanding and interpretation. The latter point being especially relevant, as forest cover data have both a technical-scientific and a political meaning and are used as relevant arguments in many discussions. In the example of Costa Rica, a general downward trend is observed up to about 1985/1990, whereas after that forest area figures are on the average at a markedly higher level. Some hypotheses for this change in the trend are discussed.     

Nitrogen isotope ratios in pine bark as an indicator of N emissions from anthropogenic sources

The article describes the use of Scots pine bark to identifynitrogen sources in eastern Germany, as well as background areas in Russia and Bulgaria, by using natural isotope ratios of total nitrogen (N_t) and individual N compoundssuch as ammonium (NH₄ ⁺), nitrate (NO₃ ^-)and amid nitrogen (amide-N). The samples collected were analysed using an elemental analyser in connection with a gas isotope mass spectrometer (EA-IRMS). Natural ¹⁵N abundances in pine bark from impact areas suggest that the ammonium accumulated on the surface of the bark is releasedfrom livestock management. Bark of Scots pines growing near agricultural land had highly depleted ¹⁵N_t values (between –8 and –12), while bark from background areas (unpolluted areas) displayed slightly negative ¹⁵N_t values (mean ¹⁵N_t = –3.8). It is assumed that part of the N adsorbed on the bark surface is mainly derived from ammonia(mean ¹⁵N_t = –40.3) escaping from livestock housing and during the application of manure. This assumption is confirmed by experiments under controlled conditions in which manure samples were spread on soil. In addition, temporal and spatial variations of ¹⁵N_t abundances in pine bark from various locations in eastern Germany as wellas pine stands in Nature Park Dübener Heath are discussed.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.     

The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.     

Time dependent influx and efflux of phenol by immobilized microbial consortium

Phenol, like many other organic solvents, is toxic to micro-organisms even at low concentrations. However, some micro-organisms can withstand this toxicity to a certain concentration. To observe the uptake mechanism of phenol, bacteria were isolatedfrom a petroleum refinery effluent and identified. Study was carried out to understand the effect of varying sub-lethal concentrations of phenol, on all the isolated individual bacterial cultures. Out of the bacteria isolated, Serratia liquefaciens was found to tolerate phenol concentration up to 1500 mg l^-1. A microbial consortium of the isolated bacteriawas formulated and immobilized. Individual cultures were also immobilized and uptake of phenol by the immobilized micro-organisms was observed in a nutrient-rich and nutrient-stressed medium containing phenol as a sole source of carbon. A time-dependent uptake of phenol was exhibited by the micro-organismsin nutrient-stressed medium, after which a sudden increase in phenol concentration occurred in the extracellular medium, till it reached back to the initial concentration. This was attributedto an active efflux mechanism adopted by the micro-organisms to withstand the toxic shock.     

Derivation of Nutrient Guidelines for Streams in Victoria, Australia

Human induced increases to nutrientconcentrations in streams have led to many agenciesdeveloping strategies and criteria for nutrientreduction. National or statewide guidelines aregenerally inappropriate, due to the natural variabilityin stream ecosystems within political boundaries. Thisstudy used an extant aquatic macroinvertebrate-basedregionalisation for the state of Victoria, Australia, asthe basis for defining regions of relatively homogeneousenvironmental character. This enabled the selection ofecologically-based regional reference sites andsubsequent characterisation of the nutrient status ofthese sites. Using an extensive biological and nutrientdata base for streams across the State, we calculated50th and 75th percentile concentrations forreference sites within each region. Using thesepercentiles in conjunction with impact and recoverystudies, we defined nutrient guidelines for each region. Although the nutrient data largely supported thebiological regionalisation, patterns in the nutrient datadid require some minor modifications for the nutrientregions. Relatively unimpacted regions with referencesites in very good-to excellent-condition were assignedguidelines largely based on the 75th percentiles. The more impacted regions, where best availablereference sites were of poorer quality, were assignedguidelines based largely on the 50th percentiles. Professional judgement and known extents of impactsacross each region provided important contributions tothe decision-making process. The derived guidelineconcentrations are comparable to several cited in theliterature and are proposed for use in monitoring,assessment and restoration targets.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).