Development of an analytical strategy based on liquid chromatography-high resolution mass spectrometry for measuring perfluorinated compounds in human breast milk: application to the generation of preliminary data regarding perinatal exposure in France

Perfluorinated compounds (PFCs) are man-made chemicals for which endocrine disrupting properties and related possible side effects on human health have been reported, particularly in the case of an exposure during the early stages of development, (notably the perinatal period). Existing analytical methods dedicated to PFCs monitoring in food and/or human fluids are currently based on liquid chromatography coupled to tandem mass spectrometry, and were recently demonstrated to present some limitations in terms of sensitivity and/or specificity. An alternative strategy dedicated to the analysis of fourteen PFCs in human breast milk was proposed, based on an effective sample preparation followed by a liquid chromatography coupled to high resolution mass spectrometry measurement (LC-HRMS). This methodology confirmed the high interest for HRMS after negative ionization for such halogenated substances, and finally permitted to reach detection limits around the pg mL(-1) range with an outstanding signal specificity compared to LC-MS/MS. The proposed method was applied to a first set of 30 breast milk samples from French women. The main PFCs detected in all these samples were PFOS and PFOA with respective median values of 74 (range from 24 to 171) and 57 (range from 18 to 102) pg mL(-1), respectively. These exposure data appeared in the same range as other reported values for European countries.     

Estimating the resuspension rate and residence time of indoor particles

Resuspension experiments were performed in a single-family residence. Resuspension by human activity was found to elevate the mass concentration of indoor particulate matter with an aerodynamic diameter less than 10 microm (PM10) an average of 2.5 times as high as the background level. As summarized from 14 experiments, the average estimated PM10 resuspension rate by a person walking on a carpeted floor was (1.4 +/- 0.6) x 10(-4) hr(-1). The estimated residence time for PM in the indoor air following resuspension was less than 2 hr for PM10 and less than 3 hr for 2-microm tracer particles. However, experimental results show that the 2-microm tracer particles stayed in the combined indoor air and surface compartments much longer (>19 days). Using a two-compartment model to simulate a regular deposition and resuspension cycle by normal human activity (e.g., walking and sitting on furniture), we estimated residence time for 2-microm conservative particulate pollutants to be more than 7 decades without vacuum cleaning, and months if vacuum cleaning was done once per week. This finding supports the observed long residence time of persistent organic pollutants in indoor environments. This study introduces a method to evaluate the particle resuspension rate from semicontinuous concentration data of particulate matter (PM). It reveals that resuspension and subsequent exfiltration does not strongly affect the overall residence time of PM pollutants when compared with surface cleaning. However, resuspension substantially increases PM concentration, and thus increases short-term inhalation exposure to indoor PM pollutants.     

Biodegradation of oxygenated and non-oxygenated imidazolium-based ionic liquids in soil

Aerobic biodegradation of ionic liquids in soil was monitored for the first time. The tests, followed over six months according to ASTM D 5988-96, were carried out on the four ionic liquids obtained from 1-R-3-methylimidazolium cations, with R=CH(3)(CH(2))(3) and CH(3)O(CH(2))(2), and the tetrafluoroborate and dicyanamide counter anions. The n-butyl derivatives, after an induction period of about two months, were found to be degradable, although the degradation rate with the dicyanamide anion was smaller. In contrast, no significant production of CO(2) was observed in the tests with the methoxyethyl derivatives. Calculations at the B3LYP/6-31G(d) level were carried out to characterize the atomic charge distributions and frontier orbital structures of 1-alkyl-3-methylimidazolium cations and point out the changes caused by replacement of a CH(2) group of the alkyl chain with an oxygen atom. The calculations predict an overall negative charge on the nitrogen atoms of the imidazolium-based cations. The energies of the highest occupied (pi) MO and lowest empty (pi( *)) MO are only slightly perturbed by the length and nature of the alkyl chain. However, the electron-donor properties of the oxy derivatives are radically increased. The HOMO becomes a lone pair orbital mainly localized on the oxygen atom, and its ionization energy is sizeably smaller than that of the outermost ring pi MO.     

Distribution of geogenic arsenic in hydrologic systems: controls and challenges

The presence of elevated concentration of arsenic (As) in natural hydrologic systems is regarded as the most formidable environmental crisis in the contemporary world. With its substantial presence in the drinking water of more than thirty countries worldwide, and with an affected population of more than 100 million, it has been termed as the largest mass poisoning in human history. In this special issue, we have tried to provide the most recent research advances on controls and challenges of this severe groundwater contaminant. The articles in this issue, originally presented in the 2006 Geological Society of America Annual Meeting, address the distribution of As in various geologic and geographic settings, the controls of redox and other geochemical parameters on its spatial and temporal variability, the influence of sedimentology and stratigraphy on its occurrence, and mechanisms controlling its mobility. The knowledge available from these studies should provide a roadmap for future research in arsenic contamination hydrology.     

Trends and events through seven centuries: the history of a wetland landscape in the Czech Republic

Environmental change can be viewed as the combined result of long-term processes and singular events. While long-term trends appear to be readily available for observation (in the form of temporal comparisons or space-for-time substitution), it is more difficult to gain information on singular events in the past, although these can be equally significant in shaping ecosystems. We examined the past 700 years in the history of a lowland wetland landscape in the Czech Republic with the help of palaeoecological, ecological, landscape archaeological, and archival data. Macrofossil and pollen data were compared to known drainage works in the area and historical climatological data. Trends and events in habitat conditions were assessed using species indicator values. Results showed that ecological succession was the general process in the study area, detected as a trend towards eutrophication, desiccation, and vegetation closure. Short-term events influenced development at the sites mainly from the second half of the nineteenth century. This is consistent with drainage history, although bias related to sample frequency cannot be excluded. On the whole, long-term trends and discrete events were complementary on different scales. We conclude that humans facilitated and accelerated background processes, which can be most likely associated with the succession of open wetlands towards terrestrial ecosystems.     

Modeling to Evaluate Contribution of Oil and Gas Emissions to Air Pollution

Oil and gas production in the Western United States has increased considerably over the past 10 years. While many of the still limited oil and gas impact assessments have focused on potential human health impacts, the typically remote locations of production in the Intermountain West suggests that the impacts of oil and gas production on national parks and wilderness areas (Class I and II areas) could also be important. To evaluate this, we utilize the Comprehensive Air quality Model with Extensions (CAMx) with a year-long modeling episode representing the best available representation of 2011 meteorology and emissions for the Western United States. The model inputs for the 2011 episodes were generated as part of the Three State Air Quality Study (3SAQS). The study includes a detailed assessment of oil and gas (O&G) emissions in Western States. The year-long modeling episode was run both with and without emissions from O&G production. The difference between these two runs provides an estimate of the contribution of the O&G production to air quality. These data were used to assess the contribution of O&G to the 8 hour average ozone concentrations, daily and annual fine particulate concentrations, annual nitrogen deposition totals and visibility in the modeling domain. We present the results for the Class I and II areas in the Western United States. Modeling results suggest that emissions from O&G activity are having a negative impact on air quality and ecosystem health in our National Parks and Class I areas.

Implications: In this research, we use a modeling framework developed for oil and gas evaluation in the western United States to determine the modeled impacts of emissions associated with oil and gas production on air pollution metrics. We show that oil and gas production may have a significant negative impact on air quality and ecosystem health in some national parks and other Class I areas in the western United States. Our findings are of particular interest to federal land managers as well as regulators in states heavy in oil and gas production as they consider control strategies to reduce the impact of development.     

One-Year Study of the Elemental Composition and Source Apportionment of PM10 Aerosols in Florence,Italy

Abstract

An extensive investigation was carried out for the characterisation of the air particulate composition in Florence. The aim was to determine the aerosol elemental concentrations, as well as to identify pollution sources. For our investigation, the external Particle-Induced X-Ray Emission–Particle-Induced γ-Ray Emission beam facility of the Istituto Nazionale di Fisica Nucleare, Van de Graaff accelerator at the Physics Department of the Florence University was used. We report the results of the analysis of a long temporal series (approximately 1 yr) of PM₁₀ particulate samples, collected on Millipore filters on a daily basis in three different sites (characterised by different urban settings). Daily concentrations of more than 20 elements were detected. The long sampling period (approximately 1 yr) allowed a comparison with the air quality recommended values and the identification of seasonal variations. Four main sources (traffic, oil-combustion, soil-dust, and wind transported sea-salt) were extracted with the help of Principal Component Analysis (PCA). An absolute PCA showed traffic to be the major source both in the high traffic site and in the urban background site.     

A Top-Down Regional Assessment of Urban Greenhouse Gas Emissions in Europe

This paper provides an account of urban greenhouse gas (GHG) emissions from 40 countries in Europe and examines covariates of emissions levels. We use a “top-down” analysis of emissions as spatially reported in the Emission Dataset for Global Atmospheric Research supplemented by Carbon Monitoring for Action from 1153 European cities larger than 50 000 population in 2000 (comprising >81 % of the total European urban population). Urban areas are defined spatially and demographically by the Global Rural Urban Mapping Project. We compare these results with “bottom-up” carbon accounting method results for cities in the region. Our results suggest that direct (Scopes 1 and 2) GHG emissions from urban areas range between 44 and 54 % of total anthropogenic emissions for the region. While individual urban GHG footprints vary from bottom-up studies, both the mean differences and the regional energy-related GHG emission share support previous findings. Correlation analysis indicates that the urban GHG emissions in Europe are mainly influenced by population size, density, and income and not by biophysical conditions. We argue that these data and methods of analysis are best used at the regional or higher scales.     

Bioaccumulation and biotransformation of arsenic compounds in Hediste diversicolor (Muller 1776) after exposure to spiked sediments

This study focused on the exposure of the common ragworm Hediste diversicolor (Müller 1776) to sediments enriched with different arsenic compounds, namely arsenate, dimethyl-arsinate, and arsenobetaine. Speciation analysis was carried out on both the spiked sediments and the exposed polychaetes in order to investigate H. diversicolor capability of arsenic bioaccumulation and biotransformation. Two levels of contamination (acute and moderate dose) were chosen for enriched sediments to investigate possible differences in the arsenic bioaccumulation patterns. The highest value of arsenic in tissues was reached after 15 days of exposure to dimethyl-arsinate (acute dose) spiked sediment (1,172?±?176 μg/g). A significant increase was also obtained in worms exposed both to arsenate and arsenobetaine. Speciation analysis showed that trimethyl-arsine oxide was the predominant chemical form in tissues of H. diversicolor exposed to all the spiked sediments, confirming the importance of this intermediate in biological transformation of arsenic.