(Table 3, Page 417) Table 3. The concentrations of Zn, Cu, Pb, Cd, Ni, Co, Ag, Mn and Fe in a soluble in 1M HCl fraction of ferromanganese nodules of Slupsk Furrow in the southern Baltic sea

The concentration of Zn, Cu, Pb, Cd, Ni, Co, Ag, Mn, Fe, Ca, Mg, K and Na in molluscs Macoma balthica, Mya arenaria, Cardium glaucum, Mytilus edulis and Astarte borealis from the southern Baltic was determined. The surface sediments and ferromanganese concretions associated with the molluscs were also analysed for concentration of these metals. Species- and region-dependent differences in the metal levels of the organisms were observed. The properties of molluscs analysed which have a tendency toward elevated biological tolerance of selected trace metals were specified. The interelement relationship between metal concentrations in the soft tissue and the shell was estimated and was discussed.

Seasonal variation of n-alkanes and polycyclic aromatic hydrocarbon concentrations in PMsub(10) samples collected at urban sites of São Paulo state, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Air sensitivity of MoS2, MoSe2, MoTe2, HfS2 and HfSe2

A surface sensitivity study was performed on different transition-metal dichalcogenides (TMDs) under ambient conditions in order to understand which material is the most suitable for future device applications. Initially, Atomic Force Microscopy and Scanning Electron Microscopy studies were carried out over a period of 27 days on mechanically exfoliated flakes of 5 different TMDs, namely, MoS2, MoSe2, MoTe2, HfS2, and HfSe2. The most reactive were MoTe2 and HfSe2. HfSe2, in particular, showed surface protrusions after ambient exposure, reaching a height and width of approximately 60 nm after a single day. This study was later supplemented by Transmission Electron Microscopy (TEM) cross-sectional analysis, which showed hemispherical-shaped surface blisters that are amorphous in nature, approximately 180–240 nm tall and 420–540 nm wide, after 5 months of air exposure, as well as surface deformation in regions between these structures, related to surface oxidation. An X-ray photoelectron spectroscopy study of atmosphere exposed HfSe2 was conducted over various time scales, which indicated that the Hf undergoes a preferential reaction with oxygen as compared to the Se. Energy-Dispersive X-Ray Spectroscopy showed that the blisters are Se-rich; thus, it is theorised that HfO2 forms when the HfSe2 reacts in ambient, which in turn causes the Se atoms to be aggregated at the surface in the form of blisters. Overall, it is evident that air contact drastically affects the structural properties of TMD materials. This issue poses one of the biggest challenges for future TMD-based devices and technologies.

The bioaccumulation of persistent contaminants by zebra mussels and their effects on state-endangered common terns

Common terns currently are listed as endangered or threatened in many states, including Illinois, Vermont, Pennsylvania, Ohio, Wisconsin, Michigan, and New York, and a species of special concern by the U.S. Fish and Wildlife Service (USFWS, 2002). The sole remaining nesting colony in Illinois is located at the Naval Station Great Lakes (NSGL) in Lake County where intensive management by the Illinois Department of Natural Resources has reduced nest predation and increased the number of eggs that hatch. However, the overall reproductive success (the number of young successfully reaching independence) has not improved. Observations of gross deformities in hatchlings (i.e. compromised feather development and cross-bill), lethargic behavior of young birds, and lesions, suggested the influence of environmental contaminants (Jablonski et al., 2005). I investigated if there were significant levels of environmental contaminants in eggs and nestlings of common terns. While there were minimal concentration of selenium, mercury, lead, and cadmium, there were large concentration of polychlorinated biphenyls (PCBs) in both the eggs and nestlings. The greater amounts of PCBs in older chicks than younger chicks suggest local contamination. In order to potentially manage the factors responsible for exposing the terns to PCBs I investigated the pathway by which PCBs were exposed to terns. The two most likely biological pathways as determined by research on Great Lake fishes were investigated. The first pathway is through atmospheric deposition of PCBs and resuspension of PCB-ladel sediment which are subsequently acquired by filter-feeding fish (e.g. alewives, Alosa pseudoharengus) and then pelagic fish (e.g. lake trout, Salvelinus namaychus) or in this case terns. The second pathway explored was via the biodeposits of zebra mussels which are consumed by round gobies (Neogobius melanostromus) and ultimately littoral fish (e.g. small-mouthed bass, Micropterus dolomieui) or terns. Because common terns breed in near-shore sites where concentrations of zebra mussels are found, as well as forage in more pelagic environments it is possible that either or both pathways may be contributing to their PCB exposure. Field experiments and stable isotope analyses demonstrated that the most likely pathway by which terns are exposed to PCBs is via alewives, similar to how apex predators such as lake trout acquire PCBs. Biodeposits from zebra mussels do not appear to be a significant factor in PCB accumulation in terns. The impact of PCB exposure on birds can vary widely, however in this situation we choise to investigate one specific behavior often affected by PCB exposure, parental attentiveness. PCBs are known to cause endocrine disruption which ultimately results in reduced brooding of young and incubation of eggs. I used temperature sensors to quantify nest temperatures and parental attentiveness during incubation. High concentrations of PCBs in our study population appear to be leading to poor parental attentiveness, and extended periods of absence during incubation and brooding, ultimately leading to poor reproductive success. Common terns are perilously close to being extirpated in Illinois and management of PCB exposure will be difficult. I propose that additional testing should be conducted to locate a site with less PCB contamination and then to move the tern colony to this location, possibly using social cues as has been done with other tern species in Illinois. PCBs are having a profound impact on common tern populations in Illinois and without moving the colony it is likely that the population will continue to decline.

Indoor air quality in Portuguese schools: levels and sources of pollutants

Indoor air quality (IAQ) parameters in 73 primary classrooms in Porto were examined for the purpose of assessing levels of volatile organic compounds (VOCs), aldehydes, particulate matter, ventilation rates and bioaerosols within and between schools, and potential sources. Levels of VOCs, aldehydes, PM2.5 , PM10 , bacteria and fungi, carbon dioxide (CO2 ), carbon monoxide, temperature and relative humidity were measured indoors and outdoors and a walkthrough survey was performed concurrently. Ventilation rates were derived from CO2 and occupancy data. Concentrations of CO2 exceeding 1000 ppm were often encountered, indicating poor ventilation. Most VOCs had low concentrations (median of individual species <5 μg/m(3) ) and were below the respective WHO guidelines. Concentrations of particulate matter and culturable bacteria were frequently higher than guidelines/reference values. The variability of VOCs, aldehydes, bioaerosol concentrations, and CO2 levels between schools exceeded the variability within schools. These findings indicate that IAQ problems may persist in classrooms where pollutant sources exist and classrooms are poorly ventilated; source control strategies (related to building location, occupant behavior, maintenance/cleaning activities) are deemed to be the most reliable for the prevention of adverse health consequences in children in schools.

Chemical changes and heavy metal partitioning in an oxisol cultivated with maize (Zea mays, L.) after 5 years disposal of a domestic and an industrial sewage sludge.

The need for solutions to minimize the negative environmental impacts of anthropogenic activities Fhas increased. Sewage sludge is composed of predominantly organic matter and can be used to improve soil characteristics, such as fertility. Therefore, its application in agriculture is an adequate alternative for its final disposal. However, there is a lack of information on its long-term effects on soil changes in tropical areas. Thus, the objectives of this study were to determine (i) the effect of sewage sludge application on heavy metal build-up in soil and maize grains and leaves, and (ii) the effects of soil amendment with sewage sludge on the chemical properties of a Brazilian oxisol. Besides the increasing levels of Zn, Cu, Ni, and Cr, amending soil with sewage sludge also alters the distribution of these metals by increasing the mobile Phases, which correlated significantly with the increase in metal extraction with two single extractants, Mehlich 1 and DTPA (Diethylene triamine pentaacetic acid). The levels of Fe, Mn, Zn, and Cu in maize grains and leaves increased with the type and rate of sewage sludge application. Nevertheless, metal build-up in soil and plants was within the allowed limits. Significant differences were also found in soil characteristics like humic fractionation with the applied sewage doses. The data obtained does not indicate any expressive drawbacks in the use of sewage sludge as a soil amendment, as the heavy metal concentrations observed are unlikely to cause any environmental or health problems, even overestimated loadings, and are in accordance with the Brazilian regulations on farming land biosolid disposal.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

A comparative study of alginate beads and an ion-exchange resin for the removal of heavy metals from a metal plating effluent

The capacity of dry protonated calcium alginate beads to sorb metals from an industrial effluent was studied and compared with a commercial ion-exchange resin (Lewatit TP 207). Both sorbents decreased zinc, nickel, iron and calcium concentrations in the effluent, and released sodium during treatment. Alginate beads removed lower amounts of heavy metals than the resin, but exhibited faster uptake kinetics. Zinc desorption from the sorbents was achieved in 30 minutes using 0.1 M HCl or 0.1 M H(2)SO(4). Desorption ratios with these acids varied between 90 and 100% for alginate, and 98 to 100% for the ion-exchange resin. Reusability tests with HCl showed that alginate beads can stand acid desorption and recover binding capacity. Overall, the comparison of dry protonated alginate beads with the resin supports the potential of the biosorbent for the treatment of industrial effluents.

Fungal spore fragmentation as a function of airflow rates and fungal generation methods

The aim of this study was to characterise and quantify the fungal fragment propagules derived and released from several fungal species (Penicillium, Aspergillus niger and Cladosporium cladosporioides) using different generation methods and different air velocities over the colonies. Real time fungal spore fragmentation was investigated using an Ultraviolet Aerodynamic Particle Sizer (UVASP) and a Scanning Mobility Particle Sizer (SMPS). The study showed that there were significant differences (p < 0.01) in the fragmentation percentage between different air velocities for the three generation methods, namely the direct, the fan and the fungal spore source strength tester (FSSST) methods. The percentage of fragmentation also proved to be dependant on fungal species. The study found that there was no fragmentation for any of the fungal species at an air velocity ≤ 0.4 m/s for any method of generation. Fluorescent signals, as well as mathematical determination also showed that the fungal fragments were derived from spores. Correlation analysis showed that the number of released fragments measured by the UVAPS under controlled conditions can be predicted on the basis of the number of spores, for Penicillium and Aspergillus niger, but not for Cladosporium cladosporioides. The fluorescence percentage of fragment samples was found to be significantly different to that of non-fragment samples (p < 0.0001) and the fragment sample fluorescence was always less than that of the non-fragment samples. Size distribution and concentration of fungal fragment particles were investigated qualitatively and quantitatively, by both UVAPS and SMPS, and it was found that the UVAPS was more sensitive than the SMPS for measuring small sample concentrations, and the results obtained from the UVAPS and SMAS were not identical for the same samples.

Characterisation of soluble components and PAH in PM10 atmospheric particulate matter in Brisbane

Fours sets of PM10 samples were collected in three sites in SEQ from December 2002 to August 2004. Three of these sets of samples were collected by QLD EPA as a part of their regular air monitoring program at Woolloongabba, Rocklea and Eagle Farm. Half of the samples were used in this study for the analysis of water-soluble ions, which are Na+, K+, Mg2+, Ca2+, NH4 +, Cl-, NO3 -, SO4 2-, F-, Br-, NO2 -, PO4 -3 and the other half was retained by QLD EPA. The fourth set of samples was collected at Rocklea, specifically for this study. A quarter of the samples obtained from this set of samples were used to analyse water-soluble ions; a quarter of the sample was used to analyse Pb, Cu, Al, Fe, Mn and Zn; and the rests were used to analyse US EPA 16 priority PAHs. The water-soluble ions were extracted ultrasonically with water and the major watersoluble anions as well as NH4 + were analysed using IC. Na+, K+, Mg2+, Ca2+ Pb, Cu, Al, Fe, Mn and Zn were analysed using ICP-AES while PAHs were extracted by acetonitrile and analysed using HPLC. Of the analysed water-soluble ions, Cl-, NO3 -, SO4 2-, Na+, K+, Mg2+ and Ca2+ were high in concentration and determined in all the samples. F-, Br-, NO2 -, PO4 -3 and NH4 + ions were lower in concentration and determined only in some samples. Na+ and Cl- were high in all samples indicating the importance of a marine source. Principal Component Analysis (PCA) was used to examine the temporal variations of the water-soluble ions at the three sites. The results indicated that there was no major difference between the three sites. However, comparing the average concentrations of ions and Cl-/Na+ it was concluded that Woolloongabba had more marine influence than the other sites. Al, Fe and Zn were detected in all samples. Al and Fe were high in all samples indicating the significance of a source of crustal matter. Cu, Mn and Pb were in low concentrations and were determined only in some samples. The lower Pb concentrations observed in the study than in previous studies indicate that the phasing-out of leaded petrol had an appreciable impact on Pb levels in SEQ. This study reports for the first time, simultaneous data on the water-soluble, metal ion and PAH levels of PM10 aerosols in Brisbane, and provides information on the most likely sources of these chemical species. Such information can be used alongside those that already exist to formulate PM10 pollution reduction strategies for SEQ in order to protect the community from the adverse effects of PM pollution.

The impact of delayed blood centrifuging, choice of collection tube, and type of assay on 25-hydroxyvitamin D concentrations

Studies have examined the associations between cancers and circulating 25-hydroxyvitamin D [25(OH)D], but little is known about the impact of different laboratory practices on 25(OH)D concentrations. We examined the potential impact of delayed blood centrifuging, choice of collection tube, and type of assay on 25(OH)D concentrations. Blood samples from 20 healthy volunteers underwent alternative laboratory procedures: four centrifuging times (2, 24, 72, and 96 h after blood draw); three types of collection tubes (red top serum tube, two different plasma anticoagulant tubes containing heparin or EDTA); and two types of assays (DiaSorin radioimmunoassay [RIA] and chemiluminescence immunoassay [CLIA/LIAISON®]). Log-transformed 25(OH)D concentrations were analyzed using the generalized estimating equations (GEE) linear regression models. We found no difference in 25(OH)D concentrations by centrifuging times or type of assay. There was some indication of a difference in 25(OH)D concentrations by tube type in CLIA/LIAISON®-assayed samples, with concentrations in heparinized plasma (geometric mean, 16.1 ng ml−1) higher than those in serum (geometric mean, 15.3 ng ml−1) (p = 0.01), but the difference was significant only after substantial centrifuging delays (96 h). Our study suggests no necessity for requiring immediate processing of blood samples after collection or for the choice of a tube type or assay.

Raman and infrared study of phyllosilicates containing heavy metals (Sb, Bi) : bismutoferrite and chapmanite.

The kaolinite-like phyllosilicate minerals bismutoferrite BiFe3+2Si2O8(OH) and chapmanite SbFe3+2Si2O8(OH) have been studied by Raman spectroscopy and complemented with infrared spectra. Tentatively interpreted spectra were related to their molecular structure. The antisymmetric and symmetric stretching vibrations of the Si-O-Si bridges,  SiOSi and  OSiO bending vibrations,  (Si-Oterminal)- stretching vibrations,  OH stretching vibrations of hydroxyl ions, and  OH bending vibrations were attributed to observed bands. Infrared bands 3289-3470 cm-1 and Raman bands 1590-1667 cm-1 were assigned to adsorbed water. O-H...O hydrogen bond lengths were calculated from the Raman and infrared spectra.

The short-term effect of air pollution on cardiovascular mortality in Tianjin, China : comparison of time series and case–crossover analyses

Background: Many studies have illustrated that ambient air pollution negatively impacts on health. However, little evidence is available for the effects of air pollution on cardiovascular mortality (CVM) in Tianjin, China. Also, no study has examined which strata length for the time-stratified case–crossover analysis gives estimates that most closely match the estimates from time series analysis. Objectives: The purpose of this study was to estimate the effects of air pollutants on CVM in Tianjin, China, and compare time-stratified case–crossover and time series analyses. Method: A time-stratified case–crossover and generalized additive model (time series) were applied to examine the impact of air pollution on CVM from 2005 to 2007. Four time-stratified case–crossover analyses were used by varying the stratum length (Calendar month, 28, 21 or 14 days). Jackknifing was used to compare the methods. Residual analysis was used to check whether the models fitted well. Results: Both case–crossover and time series analyses show that air pollutants (PM10, SO2 and NO2) were positively associated with CVM. The estimates from the time-stratified case–crossover varied greatly with changing strata length. The estimates from the time series analyses varied slightly with changing degrees of freedom per year for time. The residuals from the time series analyses had less autocorrelation than those from the case–crossover analyses indicating a better fit. Conclusion: Air pollution was associated with an increased risk of CVM in Tianjin, China. Time series analyses performed better than the time-stratified case–crossover analyses in terms of residual checking.