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.     

Drying of granulated wood ash by flue gas from saw dust and natural gas combustion

At the district heating plant of Kalmar, Sweden an on-line unit for production of granulated wood ash for nutrient recycling on forest soils is being applied. Currently, the granules are dried by hot air from an oil-fired burner. The objective of this work was to investigate how drying by flue gas affects the hardening of granules, or impacts their chemical composition and properties. Ninety-six granule samples were treated by flue gas from natural gas combustion in a laboratory pilot scale flue gas generator. CO₂, CO, O₂, C₃H₈ and NO concentrations were varied during the experiment. Additionally, some samples were treated by flue gas from combustion of sawdust at the heating plant in Kalmar. Drying by flue gases did not affect the chemical composition of granules, but minor effects were seen in their mineralogy. The carbonate content was slightly higher in granules treated with flue gas from natural gas combustion compared to the granules dried by hot air only, when measured by wet chemical methods. Results from XRD analysis imply that the calcite content is higher and the portlandite and arcanite content slightly less in granules treated with flue gas from sawdust combustion compared to the granules dried by hot air only. The results from this investigation showed no negative effects on ash granule composition or physical structure by the use of a flue as a drying medium.     

Leachability testing of metallic wastes.

The performance of two tests, a batch test and a percolation test for the characterization of waste as suggested in the EU council decision 2003/33/EC was investigated. The tests were carried out on two solid waste streams from a metal recycling industry. The concentrations of heavy metals such as Cu, Zn and Pb were more than one order of magnitude lower than the proposed limit values. Generally, batch test values were equal or higher than percolation test values. With the proposed test procedures both materials could be considered as non-dangerous wastes. The test performance was also investigated using a leachant with higher ionic strength instead of demineralized water as prescribed. The results clearly show a significant increase in the concentration of some heavy metals. Total concentrations of phenolic compounds and polychlorinated biphenyls were less than 1 p.p.m. and 2 p.p.b., respectively. The precision of the batch and the percolation tests were on average 48 and 35%, respectively.     

Influence of age,season, body condition and geographical area on concentrations of chlorinated and brominated contaminants in wild mink (Neovison vison) in Sweden

The wild mink has gained acceptance as a sentinel species in environmental monitoring. However, only limited data are available in the literature on factors driving variability in concentrations of organic pollutants in this species. This study characterizes the differences in contaminant concentrations in subcutaneous fat of male mink from four different areas in Sweden and demonstrates how age, season and body condition influence concentrations of polychlorinated biphenyl (PCB) congeners, polybrominated diphenyl ether (PBDE) congeners (including methoxylated forms, MeO-PBDEs), as well as the pesticides dichlorodiphenyldichloroethylene (DDE), chlordane and hexachlorobenzene (HCB). The data were statistically treated using multiple regression and principal component analysis. The ∑PCB concentration and concentrations of PCB congeners 138, 156, 157, 180, 170/190, 189, 194, 206, 209 as well as PBDE 153/154 varied with age. Season had an influence on ∑PCB, PBDE 47 and PBDE 153/154 concentrations, as well as concentrations of most PCB congeners, with the exception of PCB 101, 110, 141 and 182/187. Lean mink had higher concentrations of most PCBs and PBDEs than mink with larger fat depots. The analyzed pesticides (DDE, oxychlordane, HCB) showed no systematic variation with season, age or body condition. The concentrations of MeO-PBDEs were generally low and 6MeO-PBDE 47 was the most commonly detected MeO-PBDE in mink from marine, brackish and freshwater areas. The results indicate that age, season and body condition are factors that may influence the concentrations of PCBs and PBDEs, and it is thus recommended to take these factors into account when analyzing mink exposure data.     

Element associations in ash from waste combustion in fluidized bed

The incineration of MSW in fluidized beds is a commonly applied waste management practice. The composition of the ashes produced in a fluidized bed boiler has important environmental implications as potentially toxic trace elements may be associated with ash particles and it is therefore essential to determine the mechanisms controlling the association of trace elements to ash particles, including the role of major element composition. The research presented here uses micro-analytical techniques to study the distribution of major and trace elements and determine the importance of affinity-based binding mechanisms in separate cyclone ash particles from MSW combustion. Particle size and the occurrence of Ca and Fe were found to be important factors for the binding of trace elements to ash particles, but the binding largely depends on random associations based on the presence of a particle when trace elements condensate in the flue gas.     

Evaluating two test methods used for characterizing leaching properties

A standard leaching test method (EN 12457-3) was compared with a modified pHstat-column leaching test method with respect to leaching information obtained for aggregates composed of different alkaline solid wastes. In addition to a different experimental set-up, the major dissimilarity between the two test methods was the chemical equilibrium condition, i.e., in the first test the system approaches equilibrium while in the second test the system is far from equilibrium conditions. The leaching trends of sodium, calcium, chloride, sulfate and cadmium were studied. Results showed that these two test methods were comparable in respect to the total amount sodium and sulfate leached. It was also concluded that the two test methods provide different information for the constituents for which dissolution reaction is highly dependent on pH and other experimental conditions, e.g., flow rate. It was found that a batch test can be used in order to investigate the total amount leached, while a modified column-pHstat test generates more detailed results on leaching trends of some constituents.     

Leachability testing of sludge from street gullies.

Sludge from gullies, on two types of streets with different traffic intensity, was investigated using two recommended EU methods for leachability testing of waste: a two-stage batch test and an up-flow percolation test. The main purpose of this investigation was to gain more knowledge about these leaching test methods to be able to make future decisions on the general applicability of the proposed tests. A number of parameters were determined in the sludge as well as in the eluates obtained from the two leaching tests. These include pH, conductivity, dissolved organic carbon and inorganic ions as chloride ions. A number of metals as Cd, Cr, Cu, Hg, Ni and Zn, were determined by inductive coupled plasmamass spectrometry and organic compounds were screened by high performance liquid chromatography-diode array UV detection and gas chromatography-mass spectrometry. It was found that the concentrations of metals and organic compounds in the sludge were several orders of magnitudes higher than the actual eluate concentrations. For all metals the concentrations were well below the proposed limit values for non-hazardous waste included in the Council decision document 2003/33/EC. Generally, concentrations obtained in batch test were equal or higher than from percolation tests. The repeatability of the percolation and the batch test were in average 28 and 17%, respectively.     

A study of Cr(VI) in ashes from fluidized bed combustion of municipal solid waste: leaching, secondary reactions and the applicability of some speciation methods

The use of the fluidized bed technique for the combustion of municipal solid waste is a rather new concept. This type of combustor produces ash residues with somewhat different properties than the residues generated from the traditional mass burn techniques. Therefore, chemical characterization and the investigation of toxic metals behavior during ash water reactions are necessary for the safe disposal of these residues. In the present work, the total elemental composition, mineralogy and leaching behavior of ashes from the combustion of municipal solid waste in a fluidized bed combustion boiler have been investigated. The cyclone ash and, in particular, the filter ash contained considerable amounts of soluble substances, thus giving leachates with high levels of Cl-, Na+, K+, Ca2 + and Al(IIl). On the other hand, the two ash fractions taken in the boiler, the bottom and hopper ashes, were much more stable with respect to the release of salts and heavy metals. Since Cr(VI) is mobile and toxic its release from combustion residues can pose environmental problem. Even though the total Cr contents were similar in all ashes studied, the bottom ash gave about a thousand times higher levels of Cr(VI) in test leachates than the hopper, cyclone and filter ashes. However, it was found that the leached amount of Cr(VI) from the bottom ash decreased significantly when bottom ash was mixed with the hopper ash. The most probable cause for this decrease is the coupled oxidation of Al(0) to Al(III) and reduction of dissolved Cr(VI) to Cr(III). This finding that the mixing of two ash streams from the same boiler could result in the immobilization of Cr may point at a simple stabilization method. Selective extraction of water soluble, exchangeable and sparingly soluble forms of Cr(VI) was also investigated. Extraction methods were evaluated for their suitability for ash matrixes. It was found that interferences due to the presence of reducing substances in some ash materials may occur.     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

Temporal trends of polyfluoroalkyl compounds (PFCs) in liver tissue of grey seals (Halichoerus grypus) from the Baltic Sea, 1974-2008

Temporal trends of polyfluoroalkyl compounds (PFCs) were examined in grey seal (Halichoerus grypus) liver from the Baltic Sea over a period of 35 years (1974-2008). In total, 17 of 43 PFCs were found, including the perfluoroalkyl sulfonates (C₄-C₁₀ PFSAs), perfluorooctanesulfinate (PFOSi), long chain perfluoroalkyl carboxylates (C₇-C₁₄ PFCAs), and perfluoroalkyl sulfonamides (i.e., perfluorooctane sulfonamide (FOSA) and N-ethyl perfluorooctane sulfonamide (EtFOSA)), whereas saturated and unsaturated fluorotelomer carboxylates, shorter chain PFCAs and perfluoroalkyl phosphonic acids were not detected. Perfluorooctane sulfonate (PFOS) was the predominant compound (9.57-1444 ng g⁻¹ wet weight (ww)), followed by perfluorononanoate (PFNA, 0.47-109 ng g⁻¹ ww). C₆-C₈ PFSAs, PFOSi and C₇-C₁₃ PFCAs showed statistically significant increasing concentrations between 1974 and 1997, with a peak in 1997 and then decreased or levelled off (except for C₁₂ and C₁₃ PFCAs). FOSA had a different temporal trend with a maximum in 1989 followed by significant decreasing concentrations until 2008. Toxicological implications for grey seals are limited, but the maximal PFOS concentration found in this study was about 40 times lower than the predicted lowest observed effect concentrations (LOEC). The statistically significant decreasing concentrations or levelling off for several PFCs in the relative closed marine ecosystem of the Baltic Sea indicate a rapidly responding to reduced emissions to the marine environment. However, the high concentrations of PFOS and continuing increasing concentrations of the longer chain PFCAs (C₁₂-C₁₄) shows that further work on the reduction of environmental emissions of PFCs are necessary.