Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO2 with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO2 uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO2 hourly average exceeds 30% for NO2 concentrations lower than 40 microg m(-3). Nevertheless, the data quality objective of 15% is reached for 200 microg m(-3), the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 microg m(-3), the data quality objective is not met if NO is higher than 100 microg m(-3). However, the data quality objective could be reached by correcting the measurements with the bias due to interference.     

Seasonal variations in nickel and vanadium in Mont Blanc snow and ice dated from the 1960s and 1990s

Ni and V have been determined in snow and ice collected at a high altitude location (Col du D?me) near the summit of Mont Blanc on the French-Italian border; dated from the 1960s and 1990s. Ni and V were simultaneously determined by inductively coupled plasma sector field mass spectrometry. Measured concentrations range from 6 to 700 pg g(-1) and 4 to 1,100 pg g(-1) for Ni and V, respectively. The results show pronounced seasonal variations in the concentrations of both metals, with high concentration values in summer layers and much lower values for winter layers. These seasonal variations are linked especially with the existence of inversion layers during winter months. Ni and V concentrations in excess of the contributions from rock and soil dust (Ni(excess), V(excess)) appear to be mainly associated with anthropogenic inputs, with pronounced seasonal variations. Large variations in the V(excess)/Ni(excess) ratio are observed, with a higher ratio in summer than in winter. This shows differences in anthropogenic inputs at Col du D?me during the different parts of the year. The above ratio was compared with the corresponding ratios for oil combustion from stationary sources and the exhaust from gasoline and diesel engines. It appears that Ni and V concentrations at Col du D?me are probably the result of changing combinations of contributions from oil combustion for power generation, industrial and residential uses, on one side, and automobile and truck traffic, on the other side, with possibly a significant contribution from Ni smelters in Russia during winter months.     

Prenatal diagnosis of chronic granulomatous disease (CGD) in four high risk male fetuses

Prenatal diagnosis of chronic granulomatous disease (CGD) was performed in four male high risk fetuses. The male sex was previously determined by an amniotic cell karyotype. Three kinds of test were performed on fetal blood obtained by umbilical venous puncture under fetoscopy at the 20th gestational week: nitroblue tetrazolium reduction (NBT) cytochemical test with phorbol myristate acetate (PMA) as activator; luminol enhanced chemiluminescence with activation by serum opsonized zymosan (STZ) or PMA; superoxide anion (0) production by measurement of the superoxide dismutase inhibitable reduction of cytochrome c with PMA as activator. Results were compared to those obtained in six fetuses investigated for other inherited diseases. In one case, absence of granulocyte defects was confirmed at birth. In three other cases, the tests showed deficient metabolic oxidative granulocytes. The pregnancy was terminated and the CGD diagnosis was confirmed on the products of abortion. The use of three different techniques performed on whole blood for CGD prenatal diagnosis is recommended instead of a single isolated test to ensure a higher confidence in the diagnosis.     

Development of a livestock odor dispersion model: part I. Model theory and development

A livestock odor dispersion model (LODM) was developed to predict mean odor concentration, odor frequency, instantaneous odor concentration, and peak odor concentration from livestock operations. This model is based on the Gaussian fluctuating plume model and has the ability to consider the instantaneous concentration fluctuations and the differences between odor and traditional air pollutants. It can predict odor frequency from the routine hourly meteorological data input and deal with different types of sources and multiple sources. Also, the relationship between odor intensity and odor concentration was incorporated into the model.     

Distribution of PAHs and trace metals in urban stormwater sediments: combination of density fractionation,mineralogy and microanalysis

Sediment management from stormwater infiltration basins represents a real environmental and economic issue for stakeholders due to the pollution load and important tonnages of these by-products. To reduce the sediment volumes to treat, organic and metal micropollutant-bearing phases should be identified. A combination of density fractionation procedure and microanalysis techniques was used to evaluate the distribution of polycyclic aromatic hydrocarbons (PAHs) and trace metals (Cd, Cr, Cu, Ni, Pb, and Zn) within variable density fractions for three urban stormwater basin sediments. The results confirm that PAHs are found in the lightest fractions (d?d??3) whereas trace metals are equally distributed within the light, intermediary, and highest fractions (d?d?d?d?>?2.8 g cm^?3) and are mostly in the 2.3?d??3 fraction. The characterization of the five fractions by global analyses and microanalysis techniques (XRD and MEB-EDX) allowed us to identify pollutant-bearing phases. PAHs are bound to the organic matter (OM) and trace metals to OM, clays, carbonates and dense particles. Moreover, the microanalysis study underlines that OM is the main constituent responsible for the aggregation, particularly for microaggregation. In terms of sediment management, it was shown that density fractionation is not suitable for trace metals but could be adapted to separate PAH-enriched phases.     

Heterogeneous photocatalytic degradation of pesticides using decatungstate intercalated macroporous layered double hydroxides

Decatungstate W₁₀O₃₂ ^4? was efficiently intercalated between the layers of three-dimensionally ordered macroporous Mg₂Al-layered double hydroxide. The structural and textural properties of as-prepared intercalated compound were characterized using different solid-state characterization techniques such as X-ray powder diffraction, FTIR and Raman spectroscopies and electronic microscopy. The photocatalytic properties of immobilized W₁₀O₃₂ ^4? within Mg₂Al structure were investigated using 2-(1-naphthyl) acetamide (NAD) as a model of pesticide. The influence of different parameters such as amount of catalyst, pH and oxygen concentration were investigated. An optimal NAD degradation was obtained for a photocatalyst concentration of 60 mg l^?1. Under our experimental conditions, this heterogeneous photocatalyst induces photodegradation of 60 % of NAD after 17 h of irradiation at 365 nm and at pH 6.6. Interestingly, pesticide photodegradation leads to the mineralization of substrates to H₂O and CO₂ and the photocatalyst can be recycled and reused without any loss of activity over four cycles.     

The chemical exploitation of nickel phytoextraction: An environmental, ecologic and economic opportunity for New Caledonia

Herein, we explore the outlines of an innovative method based on the chemical recovery of metal-rich biomass produced in phytoextraction technologies. Taking advantage of the adaptive capacity of some New Caledonian plants to hyperaccumulate Ni²⁺ cations in their aerial parts, this technique is based on the direct use of metals derived from plants as “Lewis acid” catalysts in organic chemistry. Metallic cations contained in New Caledonian nickel hyperaccumulators are recovered through a simple cost-effective process and serve the preparation of heterogeneous catalysts used in synthetic transformations allowing access to molecules with high added-value. The design of all processes is in line with the principles of green chemistry; it is adapted to the new economic constraints; it offers a new relevant outlet for metal-rich biomass; and it represents an alternative to non-renewable mineral materials.