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.     

Antlers of Cervus elaphus as biomonitors of ⁹⁰Sr in the environment

Adequate radioprotection of the environment requires the identification of biomonitors sensitive to the variation of its radionuclide content. Due to the chemical similarities between calcium and strontium, calcified tissues of mammals are considered to be good ⁹⁰Sr biomonitors. This work considered Cervus elaphus antlers which, being shed annually, can give information about the importance of radiostrontium contamination in an ecosystem in the time period required for the growth of the antler. The samples were collected at various points of W and SW Spain. The mean value of their ⁹⁰Sr content was (70 ± 43 (S.D.)) Bq/kg d.w., range (16-218) Bq/kg d.w., and the radionuclide was evenly distributed in the different parts of the antler. There was a good correlation between the antlers’ ⁹⁰Sr content and the ⁹⁰Sr deposited in the soil. The antlers’ content of ²²⁶Ra (from the natural uranium series) and the contents of some stable elements (Ca, Mg, Sr, and K) were also determined. The values for these stable elements were practically constant in the analyzed samples, and the concentrations measured decreased in the following order:Ca » Mg > K > Sr » ⁹⁰Sr > ²²⁶Ra     

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.     

Realistic retrospective dose assessments to members of the public around Spanish nuclear facilities

In the frame of an epidemiological study carried out in the influence areas around the Spanish nuclear facilities (ISCIII-CSN, 2009. Epidemiological Study of The Possible Effect of Ionizing Radiations Deriving from The Operation of Spanish Nuclear Fuel Cycle Facilities on The Health of The Population Living in Their Vicinity. Final report December 2009. Ministerio de Ciencia e Innovación, Instituto de Salud Carlos III, Consejo de Seguridad Nuclear. Madrid. Available from: http://www.csn.es/images/stories/actualidad_datos/especiales/epidemiologico/epidemiological_study.pdf), annual effective doses to public have been assessed by the Spanish Nuclear Safety Council (CSN) for over 45 years using a retrospective realistic-dose methodology. These values are compared with data from natural radiation exposure. For the affected population, natural radiation effective doses are in average 2300 times higher than effective doses due to the operation of nuclear installations (nuclear power stations and fuel cycle facilities). When considering the impact on the whole Spanish population, effective doses attributable to nuclear facilities represent in average 3.5 × 10⁻⁵ mSv/y, in contrast to 1.6 mSv/y from natural radiation or 1.3 mSv/y from medical exposures.     

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.