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.     

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.     

High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

Quantitative PCR analysis of house dust can reveal abnormal mold conditions

Indoor mold concentrations were measured in the dust of moldy homes (MH) and reference homes (RH) by quantitative PCR (QPCR) assays for 82 species or related groups of species (assay groups). About 70% of the species and groups were never or only rarely detected. The ratios (MH geometric mean : RH geometric mean) for 6 commonly detected species (Aspergillus ochraceus, A. penicillioides, A. unguis, A. versicolor, Eurotium group, and Cladosporium sphaerospermum) were >1 (Group I). Logistic regression analysis of the sum of the logs of the concentrations of Group I species resulted in a 95% probability for separating MH from RH. These results suggest that it may be possible to evaluate whether a home has an abnormal mold condition by quantifying a limited number of mold species in a dust sample. Also, four common species of Aspergillus were quantified by standard culturing procedures and their concentrations compared to QPCR results. Culturing underestimated the concentrations of these four species by 2 to 3 orders of magnitude compared to QPCR.     

Development and validation of methods for environmental monitoring of cyclophosphamide in workplaces

Methods to monitor contamination of workplaces with antineoplastic drugs have been developed and validated. Cyclophosphamide (CP) was used as a model compound as it is one of the most commonly used antineoplastic drugs. A wipe sampling method to detect contamination with CP at surfaces was developed. A personal air sampling method to sample gas and vapour on solid sorbent tubes and particles with filters was also developed. Wipe and filter samples were extracted and sorbent samples were eluted, all with ethyl acetate. The samples were analysed with liquid chromatography tandem mass spectrometry. (2)H(6)-labelled cyclophosphamide was used as an internal standard. The between-day precision was 2-5% for wipe samples, 4-6% for sorbent samples and 3-8% for filter samples. The limit of detection was 0.02 ng CP per sample for the wipe and filter methods and 0.03 ng CP per sample for the solid sorbent method. Wipe sampling on surfaces made of different materials resulted in mean recoveries between 78-106%. The desorption recovery was between 97-102% for the wipe samples, 97% for the sorbent samples and 101% for the filter samples. Samples were stable for up to 2 months at 5 degrees C and -20 degrees C and for about 2 d at room temperature. The developed methods were applied to the measurement of contamination with CP in a hospital pharmacy. Trace amounts of CP, 1.3 and 1.4 ng, were detected on surfaces in the pharmacy.     

Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

Photocatalytic degradation of phenol

In this study photocatalytic degradation of phenol in thepresence of UV irradiated TiO₂ catalyst andH₂O₂was investigated. Effects of TiO₂ andH₂O₂concentrations and pH on photocatalytic degradation were examined. The rate constants for photocatalytic degradation wereevaluated as a function of TiO₂ and H₂O₂ concentrations and pH of the solution. It was found thatphotodegradation is an effective method for the removal of phenoland disappearance of phenol obeyed first order kinetics. The amount of CO₂h produced during photocatalytic degradation wascorresponding to the complete mineralization. Photodegradationcan be an alternative method for the treatment of phenol containing wastewaters.