Quantifying summed fullerene nC60 and related transformation products in water using LC LTQ Orbitrap MS and application to environmental samples

The application of engineered nanomaterials increases strongly. Development of analytical techniques and their application to environmental samples is essential for human and environmental risk assessment of the nanoparticles. The objective of this study was to develop a sensitive analytical method to quantify nC(60) in water, using accurate mass screening liquid chromatography-hybrid linear ion trap Orbitrap mass spectrometry. nC(60) can be transformed by oxidation, reduction and photochemical reaction. Therefore, the formation of some transformation products of nC(60) was studied as well. Finally, the developed analytical method was applied to surface water samples from several locations in the Netherlands. The developed method enabled to detect and quantify aqueous concentrations of the summed nC(60) and its transformation products as low as 5 ng/L. It was observed that nC(60) transformation products exceed quantities of the parent C(60). Despite the high sensitivity of the developed method, no nC(60) or transformation products were detected in an array of Dutch surface waters. This might be due to low emissions, losses in the aqueous phase by sedimentation, sorption or further transformation processes.     

Influence of fish size and sex on mercury/PCB concentration: importance for fish consumption advisories

Fish advisories for polychlorinated biphenyls (total-PCBs) and mercury are often given on a length-specific basis and fish sex is usually not considered. The relationship between concentration and length is well established for mercury, however its suitability for total-PCBs and the influence of sex over the large scale covered by most monitoring programs is not well known. Here we use what is perhaps the largest consistent sport fish contaminant dataset to evaluate the relationship between total-PCB/mercury and length and sex. We evaluated seven of the most commonly consumed fishes from the Canadian Great Lakes and two Ontario (Canada) inland lakes. For mercury, the relationship between concentration and length was significant (p<0.05) in most fish species and locations. For total-PCB, this relationship was also generally significant in Chinook salmon and lake trout, which are the species with the most advisories for this compound. In contrast, significant relationships were found less often for whitefish, northern pike, smallmouth bass, walleye, and especially yellow perch. However, mercury usually drives fish consumption advisories for these species. Overall, our results support the protocol of issuing contaminant advice on a length-specific basis in fish monitoring programs with reasonable confidence when at least a moderate number of samples over the natural size range of a species are included in the analysis. Sex differences were common for walleye (males>females, p<0.05) but not other species, suggesting that an equal number of male and female walleye should be used in deriving fish advisories for walleye.     

Levels of household particulate matter and environmental tobacco smoke exposure in the first year of life for a cohort at risk for asthma in urban Syracuse, NY

The Syracuse, NY, AUDIT (Assessment of Urban Dwellings for Indoor Toxics) study was designed to quantify asthma agent levels in the inner-city homes of a birth cohort whose mothers had a diagnosis of asthma. Risk of exposure to particulate matter (PM), particle number and tobacco smoke was assessed in 103 infants' homes. Repeat measurements were made in 44% of the homes. Infants also were examined on a quarterly basis during the first year of life to monitor their respiratory health and urine cotinine levels. Overall geometric mean (GM) values for PM(2.5) of 21.2 μg/m(3) and for PM(10) of 31.8 μg/m(3) were recorded in homes at visit 1. GM values for PM(2.5) and PM(10) in smoking homes were higher at 26.3 and 37.7 μg/m(3), while values in non-smoking homes were 12.7 and 21.2 μg/m(3) respectively. Fifty-four percent of mothers (55/103) smoked at some point in pregnancy (39% smoked throughout pregnancy). Environmental tobacco smoke (ETS) exposure occurred in 68% of homes during the infants' first year. Significant to this study was the size- and time-resolved monitoring of PM at 140 home visits and the classification of PM count data. PM number counts ranged from continuously low levels (little indoor activity) to continuously high counts (constant indoor activity), and recorded apparent instances of prolonged repeated cigarette smoking. Wheezing in the first year of life was recorded for 38% of the infants (39/103). Adjusted logistic regression modeling demonstrated that elevated levels of indoor PM(2.5) (≥ 15 μg/m(3)) were a significant risk factor for infant wheezing after controlling for infant gender, mothers' age and education level, season of home visit and presence of carpeting (OR 4.21; 95% CI 1.36-13.03; p=0.013). An elevated level of the nicotine metabolite cotinine in infant urine also was associated with infant wheezing after adjusting for infant gender, mothers' age and education level (OR 5.10; 95% CI 0.96-27.24; p=0.057). ETS exposure was pervasive in the AUDIT cohort and a risk for developing infants in this urban population.     

Factors affecting 210Po and 210Pb activity concentrations in mussels and implications for environmental bio-monitoring programmes

The activity of ²¹⁰Po and ²¹⁰Pb was determined in mussels of the same size (3.5-4.0 cm shell length) sampled monthly over a 17-month period at the Atlantic coast of Portugal. Average radionuclide concentration values in mussels were 759 ± 277 Bq kg⁻¹ for ²¹⁰Po (range 460-1470 Bq kg⁻¹ dry weight), and 45 ± 19 Bq kg⁻¹ for ²¹⁰Pb (range 23-96 Bq kg⁻¹ dry weight). Environmental parameters and mussel biometric parameters were monitored during the same period. Although there was no seasonal variation of radionuclide concentrations in sea water during the study period, the concentration of radionuclide activity in mussels varied seasonally displaying peaks of high concentrations in winter and low concentrations in summer. Analysis of radionuclide data in relation to the physiological Condition Index of mussels revealed that ²¹⁰Po and ²¹⁰Pb activities in the mussel (average activity per individual) remained nearly constant during the investigation period, while mussel body weight fluctuated due to fat storage/expenditure in the soft tissues. Similar variation of radionuclide concentrations was observed in mussels transplanted from the sea coast into the Tejo Estuary. However, under estuarine environmental conditions and with higher food availability throughout the year, transplanted mussel Condition Index was higher than in coastal mussels and average radionuclide concentrations were 210 ± 75 Bq kg⁻¹ (dry weight) for ²¹⁰Po and 10 ± 4 Bq kg⁻¹ (dry weight) for ²¹⁰Pb, therefore lower than in coastal mussels with similar shell length. It is concluded that the apparent seasonal fluctuation and inter-site difference of radionuclide concentrations were mostly caused by mussel body weight fluctuation and not by radionuclide body burden fluctuation. This interpretation can be extended to the apparent seasonal fluctuation in concentrations of lipophilic and lipophobic contaminants in mussels, and provides an explanation for occasional high concentrations of ²¹⁰Po and man-made contaminants measured in mussels far from pollution sources.     

Estimating sediment and caesium-137 fluxes in the Ribble Estuary through time-series airborne remote sensing

High spatial and temporal resolution airborne imagery were acquired for the Ribble Estuary, North West England in 1997 and 2003, to assess the application of time-series airborne remote sensing to quantify total suspended sediment and radionuclide fluxes during a flood and ebb tide sequence. Concomitant measurements of suspended particulate matter (SPM) and water column turbidity were obtained during the time-series image acquisition for the flood and ebb tide sequence on the 17th July 2003 to verify the assumption of a vertically well mixed estuary and thus justifying the vertical extrapolation of spatially integrated estimate of surface SPM. The ¹³⁷Cs activity concentrations were calculated from a relatively stable relationship between SPM and ¹³⁷Cs for the Ribble Estuary. Total estuary wide budgets of sediment and ¹³⁷Cs were obtained by combining the image-derived estimates of surface SPM and ¹³⁷Cs with estimates of water volume from a two-dimensional hydrodynamic model (VERSE) developed for the Ribble Estuary. These indicate that around 10,000 tonnes of sediment and 2.72 GBq of ¹³⁷Cs were deposited over the tidal sequence monitored in July 2003. This compared favourably with bed height elevation change estimated from field work. An uncertainty analysis on the total sediment and ¹³⁷Cs flux yielded a total budget of the order of 40% on the final estimate. The results represent a novel approach to providing a spatially integrated estimate of the total net sediment and radionuclide flux in an intertidal environment over a flood and ebb tide sequence.     

Aerial measurement of radioxenon concentration off the west coast of Vancouver Island following the Fukushima reactor accident

In response to the Fukushima nuclear reactor accident, on March 20th, 2011, Natural Resources Canada conducted aerial radiation surveys over water just off the west coast of Vancouver Island. Dose-rate levels were found to be consistent with background radiation, however a clear signal due to ¹³³Xe was observed. Methods to extract ¹³³Xe count rates from the measured spectra, and to determine the corresponding ¹³³Xe activity concentration, were developed. The measurements indicate that ¹³³Xe concentrations on average lie in the range of 30-70 Bq/m³.     

Depth profile of ²³⁶U/²³⁸U in soil samples in La Palma, Canary Islands

The vertical distribution of the ²³⁶U/²³⁸U isotopic ratio was investigated in soil samples from three different locations on La Palma (one of the seven Canary Islands, Spain). Additionally the ²⁴⁰Pu/²³⁹Pu atomic ratio, as it is a well establish tool for the source identification, was determined. The radiochemical procedure consisted of a U separation step by extraction chromatography using UTEVA^® Resin (Eichrom Technologies, Inc.). Afterwards Pu was separated from Th and Np by anion exchange using Dowex 1x2 (Dow Chemical Co.). Furthermore a new chemical procedure with tandem columns to separate Pu and U from the matrix was tested. For the determination of the uranium and plutonium isotopes by alpha spectrometry thin sources were prepared by microprecipitation techniques. Additionally these fractions separated from the soil samples were measured by Accelerator Mass Spectrometry (AMS) to get information on the isotopic ratios ²³⁶U/²³⁸U, ²⁴⁰Pu/²³⁹Pu and ²³⁶U/²³⁹Pu, respectively. The ²³⁶U concentrations [atoms/g] in each surface layer (∼2 cm) were surprisingly high compared to deeper layers where values around two orders of magnitude smaller were found. Since the isotopic ratio ²⁴⁰Pu/²³⁹Pu indicated a global fallout signature we assume the same origin as the probable source for ²³⁶U. Our measured ²³⁶U/²³⁹Pu value of around 0.2 is within the expected range for this contamination source.     

The state of predatory mammal populations in the impact zone of the Kalinin Nuclear Power Plant as inferred from their phene pool

The states of the populations of five dominant species of predatory mammals living in the area affected by the Kalinin Nuclear Power Plant (NPP) and in remote districts of Tver’ oblast have been compared. A total of 1120 skulls, including 708 skulls from the vicinity of the NPP, have been examined. The data on parameters characterizing similarities between the samples, the degree and structure of intrapopulation diversity, and ontogenetic stability suggest with a high probability that the Kalinin NPP has no effect on wild populations of predatory mammals.     

Geomorphometric study of the spatial organization of forest ecosystems

The use of an extended set of basic characteristics of the terrain topography for studying the spatial variation of a forest ecosystem has shown that it is significantly related to the terrain topography. The relationships with the topographic attributes determining the local hydrological and thermal conditions in the ecosystem has been paid special attention. Maps of ecosystem characteristics based on the observed relationships with topography have been calculated and drawn.