Characterization and removal of odors from refuse material

Odorous gases emitted from refuse wastes were scrubbed through activated carbon columns until odor breakthrough occured. Refuse air samples were collected at the influent and effluent ports of the columns for analysis on a gas chromatograph-mass spectrometric system and for odor determination by dynamic olfactometry. Chromatographic profiles of the gases emitted from refuse material were obtained and volatiles identified included carboxylic acids and some sulphur compounds. Organoleptic tests with a dynamic olfactometer revealed that the odor concentration of refuse air averaged about 50 sou m^–3. The adsorption capacities of four commercial grades of activated carbon for refuse odor were evaluated and compared. Results indicated that chemically impregnated activated carbons that are commonly used for odor control at sewerage facilities were less cost effective than non-chemically impregnated carbons.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.     

TPH-contaminated Mexican Refinery Soil: Health Risk Assessment and the First Year of Changes

The soil of a coastal Mexican refinery is quite contaminated, especially by hydrocarbons, with detected concentrations up to 130000 mg kg(-1) as TPHs (total petroleum hydrocarbons). The main sources of contamination are pipelines, valves, and old storage tanks, besides the land disposal of untreated hydrocarbon sediments derived from the cleaning of storage tanks. A health risk assessment (HRA) was carried out in order to measure the risk hazard indexes and clean-up standards for the refinery soil. HRA suggested the following actions to be taken: benzene concentrations must be reduced in eight of the 16 studied refinery zones to 0.0074-0.0078 mg kg(-1). Also, vanadium concentration must be reduced in two zones up to a concentration of 100 mg kg(-1). In only one of all of the studied zones, benzo(a)pyrene concentration must be reduced to 0.1 mg kg(-1). After 1 yr, TPHs showed a diminution of about 52%. Even though TPHs concentrations were variable, during 1999 the average concentrations were as much as 15.5 times the goal concentration. For year 2000, TPHs concentrations were only 7.4-fold the proposed value. For the 1999-2000 period, PAHs (polycyclic aromatic hydrocarbons) concentrations decreased by 82%. Some PAHs with 2, 3, 4, and 5 aromatic rings were removed up to 100% values.     

Paleolimnological assessment of Grove and Plow Shop Ponds, Ayer, Massachusetts, USA--a superfund site

Three sediment cores from each of severely polluted Grove and Plow Shop Ponds, Ayer, Massachusetts, USA, were dated using (210)Pb, characterized for plant macrofossil assemblages, and analyzed for H(2)O, loss-on-ignition, stable Pb isotopes, and concentrations of As, Ca, Cd, Cr, Cu, Fe, Hg, methyl-Hg, Ni, Pb, and Zn. A core from nearby kettle Spectacle Pond, Littleton, Massachusetts, was similarly characterized (except for plant macrofossil assemblages) to assess the regional air pollution signal in sediment for comparison with the six cores. Accumulation rates for metals (mass per area per year), the anthropogenic component (mass per area per year), and total accumulation of the anthropogenic component (mass per area) indicate that As, Cd, Cr, Cu, Hg, methyl-Hg, Ni, Pb, and Zn have accumulated in sediment as a consequence of point source pollution from within the drainage basins of Grove and Plow Shop Ponds. Three distinct sources of pollution are inferred. As is entering Plow Shop Pond via groundwater in the southwest. Cd, Ni, Pb, and Zn are entering the system predominantly at the eastern end of, or upstream from, Grove Pond. Pb also comes from the northwest corner of Grove Pond, the principal source of Cr, Cu, and Hg. These results are consistent with chemistry of modern surface sediments. The history of pollution extends back more than 100 years. Intra- and inter-core variability of concentrations and accumulation rates indicate that much of the pollution was likely in particulate form with little physical redistribution. Recently, concentrations and accumulation rates have generally decreased substantially for those elements present in excessive concentrations in the past. This is a consequence of accumulation of recent, less polluted sediment. In Spectacle Pond, the nearby reference lake, accumulation rates for As, Cd, Hg, and Pb, adjusted for background values and changes in sedimentation rate, increased above background starting in the late 19th century, peaked about 1980, and declined substantially to 2000. These decreases suggest that the anthropogenic (pollution) component of atmospheric deposition of these elements declined after 1980 by at least 50%(As), 80%(Cd), 80%(Hg), and 80%(Pb).     

Determination of arsenic species in fish, crustacean and sediment samples from Thailand using high performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS)

Suitable techniques have been developed for the extraction of arsenic species in a variety of biological and environmental samples from the Pak Pa-Nang Estuary and catchment, located in Southern Thailand, and for their determination using HPLC directly coupled with ICP-MS. The estuary catchment comprises a tin mining area and inhabitants of the region can suffer from various stages of arsenic poisoning. The important arsenic species, AsB, DMA, MMA, and inorganic arsenic (As III and V) have been determined in fish and crustacean samples to provide toxicological information on those fauna which contribute to the local diet. A Hamilton PRP-X100 anion-exchange HPLC system employing a step elution has been used successfully to achieve separation of the arsenic species. A nitric acid microwave digestion procedure, followed by carrier gas nitrogen addition- (N2)-ICP-MS analysis was used to measure total arsenic in sample digests and extracts. The arsenic speciation of the biological samples was preserved using a Trypsin enzymatic extraction procedure. Extraction efficiencies were high, with values of 82-102%(As) for fish and crustacean samples. Validation for these procedures was carried out using certified reference materials. Fish and crustacean samples from the Pak Pa-Nang Estuary showed a range for total arsenic concentration, up to 17 microg g(-1) dry mass. The major species of arsenic in all fauna samples taken was AsB, together with smaller quantities of DMA and, more importantly, inorganic As. For sediment samples, arsenic species were determined following phosphoric acid (1 M H3PO4) extraction in an open focused microwave system. A phosphate-based eluant, pH 6-7.5, with anion exchange HPLC coupled with ICP-MS was used for separation and detection of AsIII, AsV, MMA and DMA. The optimum conditions, identified using an estuarine sediment reference material (LGC), were achieved using 45 W power and a 20 minute heating period for extraction of 0.5 g sediment. The stability and recovery of arsenic species under the extraction conditions were also determined by a spiking procedure which included the estuarine sediment reference material. The results show good stability for all species after extraction with a variability of less than 10%. Total concentrations of arsenic in the sediments from the Pak Pa-Nang river catchment and the estuary covered the ranges 7-269 microg g(-1)and 4-20 [micro sign]g g(-1)(dry weight), respectively. AsV was the major species found in all the sediment samples with smaller quantities of AsIII. The presence of the more toxic inorganic forms of arsenic in both sediments and biota samples has implications for human health, particularly as they are readily 'available'.     

Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Natural mercury enrichment in a minerogenic fen--evaluation of sources and processes

Mercury (Hg) records in natural archives such as peat bogs are often used to evaluate anthropogenic or climatic influences on atmospheric Hg deposition. In this context, there is an ongoing discussion about natural sources or processes of Hg enrichment in natural archives. In the present study we estimated Hg fluxes from rock weathering, direct atmospheric deposition and from indirect atmospheric deposition in the catchment of a pristine minerogenic fen (GC2) located in the Magellanic Moorlands, southernmost Chile. The Hg record in the bog covers 11 174 cal. (14)C years and shows Hg concentrations of up to 570 [micro sign]g kg(-1) with an average of 268 [micro sign]g kg(-1). Hg was found to be enriched in the peat by a factor of 81 if compared to the mean Hg concentrations in the rocks of the catchment (3.2 [micro sign]g kg(-1)). Hg and also Pb, Fe, and As were found to be enriched predominately in goethite layers indicating high retention of these elements in the bog by iron oxyhydrates. It could also be demonstrated that the high peat decomposition rates in minerogenic bogs can increase the Hg concentrations in the minerogenic peat by a factor of approximately 2 at the same atmospheric Hg deposition rate if compared to ombrotrophic sites. This study has shown that Hg in minerogenic peat can be naturally enriched especially through the retention by autochthonous formed goethite and can be a solely internal process which does not require increased external Hg fluxes.     

Naphthalene and its biomarkers as measures of occupational exposure to polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAH) include compounds with two or more fused benzene rings, many of which are carcinogens. Industrial sources produce hundreds of PAH, notably in the coke- and aluminium-producing industries. Because PAH are distributed at varying levels between gaseous and particulate phases, exposure assessment has been problematic. Here, we recommend that occupational exposures to naphthalene be considered as a potential surrogate for occupational PAH exposure for three reasons. Naphthalene is usually the most abundant PAH in a given workplace; naphthalene is present almost entirely in the gaseous phase and is, therefore, easily measured; and naphthalene offers several useful biomarkers, including the urinary metabolites 1- and 2-hydroxynaphthalene. These biomarkers can be used to evaluate total-body exposure to PAH, in much the same way that 1-hydroxypyrene has been applied. Using data from published sources, we show that log-transformed airborne levels of naphthalene are highly correlated with those of total PAH (minus naphthalene) in several industries (creosote impregnation: Pearson r= 0.815, coke production: r= 0.917, iron foundry: r= 0.854, aluminium production: r= 0.933). Furthermore, the slopes of the log-log regressions are close to one indicating that naphthalene levels are proportional to those of total PAH in those industries. We also demonstrate that log-transformed urinary levels of the hydroxynaphthalenes are highly correlated with those of 1-hydroxypyrene among coke oven workers and controls (r= 0.857 and 0.876), again with slopes of log-log regressions close to one. These results support the conjecture that naphthalene is a useful metric for occupational PAH exposure. Since naphthalene has also been shown to be a respiratory carcinogen in several animal studies, it is also argued that naphthalene exposures should be monitored per se in industries with high levels of PAH.