Low cost measurements of nitrogen and sulphur dry deposition velocities at a semi-alpine site: gradient measurements and a comparison with deposition model estimates

The conditional time averaged gradient method was used to measure air-surface exchange of nitrogen and sulphur compounds at a semi-alpine site in Southern Norway. Dry deposition velocities were then obtained from the bi-weekly concentration gradient measurements. Annual deposition velocities were found to be 1.4, 11.8 and 4.0 mm s(-1) for NH3, HNO3 and SO2, respectively, if all data were included, and to be 10.8, 11.8 and 13.0 mm s(-1), respectively, if only positive values were included. Measured deposition velocities were compared to two sets of values estimated from a big-leaf dry deposition module applying to two different land types (short grass and forbs, and tundra), driven by measured micrometeorological parameters. The deposition module gives reasonable values for this site throughout the year, but does not reproduce the large variability as shown in the measured data. No apparent seasonal variations were found from either measurements or module estimates due to the very low productivity of the studied area.     

PUMP-CTD-System for trace metal sampling with a high vertical resolution. A test in the Gotland Basin, Baltic Sea

It is a great challenge to sample seawater across interfaces, for example the halocline or the redoxcline, to investigate trace metal distribution. With the use of 10l sampling bottles mounted to a wire or a CTD-Rosette it is possible to obtain a maximum vertical resolution of 5m. For the detection of small vertical structures in the vertical distribution of trace metals across the redoxcline, the CTD-Bottle-Rosette is not sufficient. Therefore, a PUMP-CTD-System was developed, which enables water sampling with high resolution (1m maximum) along a vertical profile. To investigate the suitability and possible contamination sources of this device two experiments were carried out in the Gotland Basin. The first experiment consisted of two separate profiles. The first profile was obtained with the CTD-Bottle-Rosette and the second with the PUMP-CTD-System. Both were taken from the bottom to the surface water layer. The second experiment was a combined profile obtained from the surface to the bottom with the PUMP-CTD-System attached to the CTD-Bottle-Rosette. Concentrations of dissolved Pb, Cd, Cu, Zn, Fe, Mn, Co and Ni from the "Niskin Bottles" and from the PUMP were measured and compared for each investigation. We demonstrate that it is useful to perform vertical sampling from lower to higher concentrations, e.g. surface to bottom in this environment, and that a longer flushing is required for sampling seawater in the anoxic bottom water. A comparison of the two systems for oxygen and hydrogen sulphide measurements showed an improvement of the precision and the quality of the sampling when using the PUMP. Thus, metal speciation at the oxic-anoxic gradient zone and on a high vertical resolution will be accessible. As concentrations of dissolved Pb, Cd, Cu, Zn, Co, Ni, Fe and Mn in seawater sampled with both devices were in the same range, we conclude that the PUMP-CTD-System is well suited to sample seawater for trace metal analyses.     

Atmospheric pollutants monitoring by analysis of epiphytic lichens

The Canoparmelia texana epiphytic lichenized fungi was used to monitor atmospheric pollution in the S?o Paulo metropolitan region, SP, Brazil. The cluster analysis applied to the element concentration values confirmed the site groups of different levels of pollution due to industrial and vehicular emissions. In the distribution maps of element concentrations, higher concentrations of Ba and Mn were observed in the vicinity of industries and of a petrochemical complex. The highest concentration of Co found in lichens from the S?o Miguel Paulista site is due to the emissions from a metallurgical processing plant that produces this element. For Br and Zn, the highest concentrations could be associated both to vehicular and industrial emissions. Exploratory analyses revealed that the accumulation of toxic elements in C. texana may be of use in evaluating the human risk of cardiopulmonary mortality due to prolonged exposure to ambient levels of air pollution.     

Heavy metal accumulation in Littoraria scabra along polluted and pristine mangrove areas of Tanzania

The periwinkle Littoraria scabra was collected at polluted and pristine mangrove sites along the Tanzanian coastline, including Msimbazi, Mbweni (i.e. Dar es Salaam) and Kisakasaka, Nyamanzi and Maruhubi (i.e. Zanzibar). Periwinkles were morphologically characterized, sexed and their heavy metal content was determined using ICP-MS. Analysis revealed that L. scabra from polluted areas contained higher soft tissue heavy metal levels, were significantly smaller and weighed less compared to their conspecifics from the unpolluted mangroves. The current morphological observations may be explained in terms of growth and/or mortality rate differences between the polluted and non-polluted sites. Although a variety of stressors may account for these adverse morphological patterns, our data suggest a close relationship with the soft tissue heavy metal content. Compared to soft tissue heavy metal levels that were measured in L. scabra along the same area in 1998, most metals, except for arsenic, chromium and iron have decreased dramatically.     

Monitoring contaminants from oil production at sea by measuring gill EROD activity in Atlantic cod (Gadus morhua)

An ex vivo gill EROD assay was applied in Atlantic cod (Gadus morhua) as a biomarker for waterborne CYP1A-inducing compounds derived from oil production at sea. Exposure to nominal concentrations of 1 ppm or 10 ppm North Sea crude oil in a static water system for 24 h caused a concentration-dependent gill EROD induction. Further, exposure of cod for 14 days to environmentally relevant concentrations of produced water (PW, diluted 1:200 or 1:1000) from a platform in the North Sea using a flow-through system resulted in a concentration-dependent induction of gill EROD. Crude oil (0.2 ppm) from the same oil field also proved to induce EROD. Finally, gill EROD activity in cod caged for 6 weeks at 500-10 000 m from two platforms outside Norway was measured. The activities in these fish were very low and did not differ from those in fish caged at reference sites.     

Effect of mono-ortho and di-ortho substituted polychlorinated biphenyl (PCB) congeners on leopard frog survival and sexual development

We tested the effect of mono-ortho and di-ortho PCB congeners on northern leopard frog (Rana pipiens) hatching success, survival and sexual development. Embryos and tadpoles were exposed to two levels (0.5 and 50 microg/l) of two PCBs. PCBs 101 and 70 were selected because they were present in amphibians collected in the Fox River-Green Bay ecosystem and they have the theoretical structural requirements to be able to bind to the estrogen receptor and mediate estrogenic responses. The exposure of leopard frog embryos and tadpoles to PCB 70 and 101 did not significantly affect hatchability, survival, deformities or growth. There were significant departures from the expected 50:50 sex ratio in tadpoles/froglets exposed to PCB 101 and PCB 70. In all the cases of significant departure, the bias was towards higher number of females. Decrease in the proportion of male gonads and increase in the proportion of intersex gonads were observed with increasing PCB tissue concentrations. The effects of PCB congeners on sexual differentiation occur at concentrations higher than observed in frogs in the Fox River/Green Bay ecosystem.     

Comparative study of chromium biosorption by red, green and brown seaweed biomass

Dried biomass of the macroalgae Fucus vesiculosus and Fucus spiralis (brown), Ulva spp. (comprising Ulva linza, Ulva compressa and Ulva intestinalis) and Ulva lactuca (green), Palmaria palmata and Polysiphonia lanosa (red) were studied in terms of their chromium biosorption performance. Metal sorption was highly pH dependent with maximum Cr(III) and Cr(VI) sorption occurring at pH 4.5 and pH 2, respectively. Extended equilibrium times were required for Cr(VI) binding over Cr(III) binding (180 and 120min, respectively) thus indicating possible disparities in binding mechanism between chromium oxidation states. The red seaweed P. palmata revealed the highest removal efficiency for both Cr(III) and Cr(VI) at low initial concentrations. However, at high initial metal concentrations F. vesiculosus had the greatest removal efficiency for Cr(III) and performed almost identically to P. lanosa in terms of Cr(VI) removal. The Langmuir Isotherm mathematically described chromium binding to the seaweeds where F. vesiculosus had the largest q(max) for Cr(III) sorption (1.21mmol g(-1)) and P. lanosa had the largest Cr(VI) uptake (0.88mmol g(-1)). P. palmata had the highest affinity for both Cr(III) and Cr(VI) binding with b values of 4.94mM(-1) and 8.64mM(-1), respectively. Fourier transform infrared analysis revealed interactions of amino, carboxyl, sulphonate and hydroxyl groups in chromium binding to Ulva spp. The remaining seaweeds showed involvement of these groups to varying degrees as well as ether group participation in the brown seaweeds and for Cr(VI) binding to the red seaweeds.     

Analysis of perfluorooctanoate (PFOA) and other perfluorinated compounds (PFCs) in the River Po watershed in N-Italy

C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).     

Polychlorinated biphenyls (PCBs) and hydroxy-PCBs in adipose tissue of women in Southeast Spain

Polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) were investigated in human adipose tissue samples collected from 20 women undergoing surgery. Mean sum of PCB and sum of OH-PCB levels were 737ng/g of lipid and 8pg/g of lipid, respectively. Among PCBs, congeners 180, 153, 138 and 170 were the most frequent and abundant, and together constituted 72% of the total amount of PCBs in adipose tissue. The PCB congener pattern and the frequencies and concentrations of non-dioxin-like and non-hydroxylated congeners observed in adipose tissue were similar in distribution and order of magnitude to the profile previously published in Spain but lower than that found in other European countries. Among OH-PCB congeners studied, 4-OH-PCB 107/118 was found at the highest concentrations followed by 3'-OH-PCB 180 and 3-OH-PCB 138. To date, no information on levels of PCB metabolites in the Spanish population is available for comparison. These three predominant OH-PCBs contributed 97% of all OH-PCBs. Twelve dioxin-like PCBs contributed around 8% of the total PCB exposure, and all were present in all study subjects. Further research is required to determine trends in human exposure to PCBs and OH-PCBs and how existing banning measures affect exposure.     

Sulphur transformation and deposition in the rhizosphere of Juncus effusus in a laboratory-scale constructed wetland

Sulphur cycling and its correlation to removal processes under dynamic redox conditions in the rhizosphere of helophytes in treatment wetlands are poorly understood. Therefore, long-term experiments were performed in laboratory-scale constructed wetlands treating artificial domestic wastewater in order to investigate the dynamics of sulphur compounds, the responses of plants and nitrifying microorganisms under carbon surplus conditions, and the generation of methane. For carbon surplus conditions (carbon:sulphate of 2.8:1) sulphate reduction happened but was repressed, in contrast to unplanted filters mentioned in literature. Doubling the carbon load caused stable and efficient sulphate reduction, rising of pH, increasing enrichment of S(2-) and S(0) in pore water, and finally plant death and inhibition of nitrification by sulphide toxicity. The data show a clear correlation of the occurrence of reduced S-species with decreasing C and N removal performance and plant viability in the experimental constructed wetlands.