Trace metals in arcid clam Scapharca inaequivalvis: effects of molluscan extracts on bioluminescent bacteria

The relationship between a supposed effect of molluscan extracts on bioluminescent bacteria and metal concentrations in the extracts was investigated. For this purpose a biotoxicological assay based on bioluminescent bacteria (BLB) and extracts from metal exposed molluscs, Scapharca inaequivalvis, was optimized to monitor Cd and Cu marine pollution. Cu and Cd concentrations increased in tissues of experimentally exposed molluscs. Molluscan extracts inhibited the bacterial luminescence, the inhibition decreasing as the time of mollusc exposure to metals increased, suggesting a reduction of the "bioactive" metals. In regard to the use of BLB test in environmental monitoring, the analysis of Cu, Cd, and metallothionein (MT) was first performed in tissues from molluscs collected in three different areas of Northern Adriatic Sea. Metal concentrations reached maximum values in the gills, while Cd was mostly bound to MT in the kidney. Significant differences in metals and MT concentrations were found depending on the sampling sites. The biotoxicological assay resulted slightly correlated with the biochemical parameters.     

Biogenic sulphide plays a major role on the riboflavin-mediated decolourisation of azo dyes under sulphate-reducing conditions

The effect of high concentrations of sulphate on the reductive decolourisation of different azo dyes by anaerobic sludge was studied in batch cultures. Sludge cultures were pre-incubated under sulphate-reducing conditions prior addition of dyes. Little or no effects of sulphate (5-10 g sulphate l(-1)) on the rate of decolourisation of Reactive Orange 14 (RO14), Direct Blue 53 (DB53) and Direct Blue 71 (DB71) were observed when no external redox mediator was provided. However, an increase in sulphate concentration, in the presence of riboflavin (20 microM), enhanced the decolourisation of all dyes. The first-rate constant of decolourisation (k) was increased up to 2-, 3.6- and 2-fold for RO14, DB53 and DB71, respectively, by supplying high sulphate concentrations, compared to the controls lacking sulphate, in the presence of the redox mediator. Sulphate reduction did not take place during the course of azo reductions, but was only evident before dye addition and after complete decolourisation, suggesting azo dyes reduction out-competed sulphate reduction for the available reducing equivalents. The experimental data suggest that reduction of azo dyes by riboflavin, which had been reduced by biogenic sulphide, was the major mechanism implicated during decolourisations, which was corroborated by abiotic incubations. Riboflavin greatly accelerated the abiotic reduction of RO14, so that the k value was increased up to 44-fold compared to the control lacking riboflavin.     

The behaviour of residual contaminants at a former station site,Antarctica

In 1994, New Zealand's only mainland Antarctic base, Vanda Station, was removed from the shores of Lake Vanda, in the McMurdo Dry Valleys region of southern Victoria Land, Antarctica. Residual chemical contamination of the station site has been identified, in the form of discrete fuel spills, locally elevated Pb, Zn, Ag and Cd concentrations in soil and elevated Cu, Ni, Co and phosphate concentrations in suprapermafrost fluids in a gully formerly used for domestic washing water disposal. Pathways for contaminant transfer to Lake Vanda, potential environmental impacts and specific remediation/monitoring options are considered. While some contaminants (particularly Zn) could be selectively leached from flooded soil, during a period of rising lake level, the small area of contaminated soils exposed and low level of contamination suggests that this would not adversely affect either shallow lake water quality or the growth of cyanobacteria. Phosphate-enhanced growth of the latte may, however, be a visible consequence of the minor contamination occurring at this site.     

Evaluation of VOC measurments in the EXPOLIS study. Air Pollution Exposure Distributions within Adult Urban Urban Populations in Europe

Personal exposures and microenvironment concentrations of 30 target VOCs were measured for 401 participants living in five European cities as a part of the EXPOLIS (Air Pollution Exposure Distributions within Adult Urban Populations in Europe) study. Measurements in Basel used an active charcoal (Carbotech) adsorbent as opposed to the Tenax TA used in the other study centres. In addition, within each centre, personal and microenvironment VOC sampling required different sampling pumps and, because of different sampling durations, different sampling flow rates. Thus, careful testing of the sampling and analysis procedures was required to ensure accuracy and comparability of collected data. Monitor comparison tests using Tenax TA showed a mean VOC concentration ratio of 0.95 between the personal and microenvironment monitors. The LODs for the target VOCs using Tenax TA ranged from 0.7 to 5.2 microg m(-3). The LODs for the 14 target compounds quantifiable using Carbotech ranged from 0.9 to 3.2 microg m(-3). Tenax TA field blanks showed no remarkable contamination with the target VOCs, except benzaldehyde, a known artefact with this adsorbent. Thus, the diffusion barrier system used prevented contamination of Tenax TA samples by passive diffusion during non-sampling periods. Duplicate and parallel evaluations of the Tenax TA and Carbotech showed an average difference of < 17% in VOC concentrations within the sampling methods, but a systematic difference between the methods (Tenax TA: Carbotech concentration ratio = 1.18-2.36). These field evaluations and quality assurance tests showed that interpretation and comparison of the results in any VOC monitoring exercise should be done on a compound by compound basis. It is also apparent that carefully planned and realised QA and QC (QA/QC) procedures are needed in multi-centre studies, where a common sampling method and laboratory analysis technique are not used, to strengthen and simplify the interpretation of observed VOC levels between participating centres.     

Determinations of PCB within a project to develop cleanup methods for PCB-containing elastic sealant used in outdoor joints between concrete blocks in buildings

Determinations of PCB were carried out as part of a project aimed at developing cleanup methods for PCB-containing elastic sealant used in outdoor joints between concrete blocks. The goals of the project were to develop methods, which minimise the spread of PCB to the outdoor environment and to indoor air, and which keep the PCB levels as low as reasonably possible in the workplace environment whilst removing the elastic sealant. The following PCB determinations were carried out: (1) concentration in the elastic sealant; (2) concentration in the concrete close to the sealant; (3) concentration in soil; (4) concentration in the indoor air; and (5) concentration in the air in the workplace environment. The cleanup process consisted of a number of different steps: (1) cutting the elastic sealant with an oscillating knife; (2) grinding the concrete with a mechanical machine; (3) sawing the concrete with a mechanical saw and (4) cutting the concrete with a mechanical chisel. In all these different steps a high capacity vacuum cleaner connected to the machines was used. The elastic sealant contained 4.7 to 8.1% total PCB of a technical product with a composition most similar to Clophene A40. The concrete close to the sealant (first 2 mm) contained 0.12 and 1.7% total PCB at two different places. The pattern of the PCB in the concrete resembled that of the sealant. PCB concentrations in the soil from the ground close to the building were 0.1 and 0.3 ppm at two different places before the remedial action. The source of the PCB in the soil is most likely the sealant as the PCB pattern is similar for the two materials. The PCB levels in the workplace air at the beginning of the project, when the techniques were not fully developed, were generally above the occupational exposure limit of 10 micrograms m-3 (up to 120 micrograms m-3). Later when the techniques were optimised to better take care of dust and gases produced during the cutting and grinding etc., the levels were below or close to 10 micrograms m-3. The pattern of the PCB in the workplace air was different from that of the sealant and contained higher levels of lighter components. The PCB concentrations in the indoor air were measured before and during the remedial process. The levels were around 600 ng m-3 and there was no significant increase during the removal of the sealant. The PCB level after the remedial action will be measured later. The pattern of the PCB in the indoor air was different from that of the sealant as well as from that of the workplace air. Higher levels of the lighter PCB were present indoors compared to the composition in both workplace air and in sealant. Extracts of PCB were analysed by GC-MS with a SIM method (selected ion monitoring). Standard procedures were used for extraction of solid materials. For the air samples an OVS tube was used with XAD-2 as adsorbent. The filter and adsorbent were extracted with toluene. This work shows that it is important to perform remedial action of PCB-containing elastic sealant as: (1) there is a spread of PCB to the indoor air giving high enough concentrations to make this the main PCB load on humans living in the apartments studied in this project; (2) large amounts are spread to the soil from these sealants; and (3) many of the PCB-containing elastic sealants used need to be changed from a functional perspective.     

Measurement of organic contaminants and biological effects in Scottish waters between 1999 and 2005

Concentrations of organic contaminants were determined in sediment and fish collected annually at six sites around Scotland between 1999 and 2005, as part of the UK National Marine Monitoring Programme. Polycyclic aromatic hydrocarbons (PAHs) and chlorobiphenyls (CBs) were measured in sediment, while CBs and ethoxyresorufin-O-deethylase (EROD) activities were measured in the fish. Highest PAH concentrations in sediment were found at sites where higher coastal influences would be expected (e.g., Clyde and Solway) and four of the six sites gave PAH concentrations above OSPAR background assessment concentrations (BACs). A significant downward trend in the median total PAH concentrations, normalised to total organic carbon (TOC), was found at one of the six sites (Minches). The PAH profiles at all sites were consistent over the 6 year period, indicating that the sites are relatively stable and PAH sources are not changing. There was an indication of a greater petrogenic input on the west coast, with sediment from the Clyde, Solway and Minches having a greater proportion of 2- and 3-ring PAHs and a lower proportion of 5-ring PAHs. CB concentrations at all sites were low compared with UK estuarine sites and similar to sediment from more remote areas: however, BACs were exceeded. No significant trends were detected in either the sediment CB concentrations or patterns at any of the six sites. CB concentrations were significantly higher in fish liver collected from the Clyde. Concentrations at the other five sites were low, with the majority of samples having concentrations for the ICES7 CBs of <500 microg kg(-1) lipid weight. However, individual CB concentrations were still above the BACs. Hepatic EROD activities were measured in male plaice from 2002-2005 and were generally low (<10 pmol min(-1) mg protein(-1)). No temporal trends were detected in either CB concentrations or the EROD activity.     

Optimizing a GC-MS method for screening of Stachybotrys mycotoxins in indoor environments

Presence of Stachybotrys chartarum in indoor environments has been linked to building-associated disease, however, the causative agents are unknown. Verrucarol (VER) and trichodermol (TRID) are hydrolysis products of some major S. chartarum mycotoxins, i.e. macrocyclic trichothecenes and trichodermin. We optimized gas chromatography-mass spectrometry (GC-MS) methods for detecting VER and TRID in S. chartarum-contaminated indoor environmental samples. Heptafluorobutyryl derivatives of both VER and TRID exhibited little MS fragmentation and gave much higher detection sensitivity (sub-picogram injected onto the GC column), both in GC-MS and GC-MSMS, than trimethylsilyl derivatives. Optimal detection sensitivity and specificity was achieved by combining chemical ionization and negative ion (NICI) detection with MSMS. With this method, VER and TRID were detected in building materials colonized by S. chartarum and TRID was demonstrated in dust settled in the breathing zone in a house where an inner wall was colonized. In summary, we have shown that NICI-GC-MSMS can be used to demonstrate mycotoxins in house dust in S. chartarum-contaminated dwellings.     

Role of volcanic dust in the atmospheric transport and deposition of polycyclic aromatic hydrocarbons and mercury

The role of volcanic ash as scavenger of atmospheric pollutants, in their transport and final deposition to the ground is examined. Attention is focused on polycyclic aromatic hydrocarbons (PAHs) and on particulate mercury (Hgp). The ash-fall deposits studied belong to the 2001 and 2002 eruptive activity of Mount Etna, Southern Italy, and were investigated at three (2001) and four (2002) sites downwind of the major tephra dispersal pattern. The dry deposition of mercury and PAHs was determined, and, in particular, a downward flux to the ground of PAHs (approximately 7.29 microg m(-2) per day) and mercury (750 ng m(-2) per day) was estimated in Catania from October 26 to October 28, 2002. Finally, evidence on the anthropogenic origin of PAHs scavenged from the troposphere by volcanic ash is supported by the analysis of PAH compositions in granulometrically homogeneous fractions.     

Stability and storage problems in organotin speciation in environmental samples

The stability of both tributyltin (TBT) and triphenyltin (TPT) in water, sediment, oysters and cockles was studied over a period of 18 months using several storage conditions. Butyltins were stable in unacidified sea-water stored in polycarbonate bottles in the dark at 4 degrees C for 7 months, but half of the TBT concentration was lost after 540 d. A comparable preservation time was achieved for butyltins stored on C18 cartridges at room temperature. However, phenyltins extracted from sea-water were stable for only 60 d stored on cartridges and even more pronounced losses (about 90% after 540 d) occurred when they were stored in either polycarbonate or Pyrex glass bottles. Losses of organotins were observed in sediments after air drying and pasteurization treatments using a freeze-dried sediment as a comparator, whereas both butyltin and phenyltin species remained stable in sediments stored at -20 degrees C for the 18 months tested, irrespective of the treatment used for stabilization. Air drying followed by pasteurization was shown to be superior to other treatments for the stabilization of organotin compounds in sediments stored at higher temperatures, but 30% of TBT was lost after 540 d at 25 degrees C. Finally, butyltins were stable in both frozen cockles and oysters in the dark over a 7 month period and in freeze-dried samples stored at 4 degrees C for 5 months, but TBT losses of about 70% were observed after 540 d.     

Fast characterization of non domestic load in urban wastewater networks by UV spectrophotometry

Urban wastewater treatment plant efficiency, as well as biosolid quality, depends on urban wastewater quality, which can be affected by non domestic discharges (industrial, commercial etc.). The characterization of wastewater quality and non domestic discharge is complex, expensive and time consuming. However, these discharges must be controlled and reduced if possible. The development of a simple and fast methodology, namely based on alternative methods such as UV spectrophotometry, has been carried out and applied to different areas of a medium sized town of Southern Québec (Canada). Several autosamplers and on line/on site measurements have been used in critical control points of the network areas, for a dry weather campaign in four areas (industrial, commercial, hospital and university). The flow rate study, completed by the exploitation of conductivity measurements and the qualitative examination of UV spectra allows the discrimination of non domestic loads and their variability study from one point to another. The identification of critical discharges and organic shock loads has been possible with low investment, and mitigation actions have been proposed.