Long-term relationships among pesticide applications, mobility, and soil erosion in a vineyard watershed.

Agricultural pesticide use has increased worldwide during the last several decades, but the long-term fate, storage, and transfer dynamics of pesticides in a changing environment are poorly understood. Many pesticides have been progressively banned, but in numerous cases, these molecules are stable and may persist in soils, sediments, and ice. Many studies have addressed the question of their possible remobilization as a result of global change. In this article, we present a retro-observation approach based on lake sediment records to monitor micropollutants and to evaluate the long-term succession and diffuse transfer of herbicides, fungicides, and insecticide treatments in a vineyard catchment in France. The sediment allows for a reliable reconstruction of past pesticide use through time, validated by the historical introduction, use, and banning of these organic and inorganic pesticides in local vineyards. Our results also revealed how changes in these practices affect storage conditions and, consequently, the pesticides' transfer dynamics. For example, the use of postemergence herbicides (glyphosate), which induce an increase in soil erosion, led to a release of a banned remnant pesticide (dichlorodiphenyltrichloroethane, DDT), which had been previously stored in vineyard soil, back into the environment. Management strategies of ecotoxicological risk would be well served by recognition of the diversity of compounds stored in various environmental sinks, such as agriculture soil, and their capability to become sources when environmental conditions change.

Down-regulation of interferon signature in systemic lupus erythematosus patients by active immunization with interferon α-kinoid.

OBJECTIVE: We developed interferon-α-kinoid (IFN-K), a drug composed of inactivated IFNα coupled to a carrier protein, keyhole limpet hemocyanin. In human IFNα-transgenic mice, IFN-K induces polyclonal antibodies that neutralize all 13 subtypes of human IFNα. We also previously demonstrated that IFN-K slows disease progression in a mouse model of systemic lupus erythematosus (SLE). This study was undertaken to examine the safety, immunogenicity, and biologic effects of active immunization with IFN-K in patients with SLE. METHODS: We performed a randomized, double-blind, placebo-controlled, phase I/II dose-escalation study comparing 3 or 4 doses of 30 µg, 60 µg, 120 µg, or 240 µg of IFN-K or placebo in 28 women with mild to moderate SLE. RESULTS: IFN-K was well tolerated. Two SLE flares were reported as serious adverse events, one in the placebo group and the other in a patient who concomitantly stopped corticosteroids 2 days after the first IFN-K dose, due to mild fever not related to infection. Transcriptome analysis was used to separate patients at baseline into IFN signature-positive and -negative groups, based on the spontaneous expression of IFN-induced genes. IFN-K induced anti-IFNα antibodies in all immunized patients. Notably, significantly higher anti-IFNα titers were found in signature-positive patients than in signature-negative patients. In IFN signature-positive patients, IFN-K significantly reduced the expression of IFN-induced genes. The decrease in IFN score correlated with the anti-IFNα antibody titer. Serum complement C3 levels were significantly increased in patients with high anti-IFNα antibody titers. CONCLUSION: These results show that IFN-K is well tolerated, immunogenic, and significantly improves disease biomarkers in SLE patients, indicating that further studies of its clinical efficacy are warranted.

Investigation of organic matter entrapped in synthetic carbonates--a multimethod approach.

Organic matter (OM) entrapped in calcite is regularly used for environmental studies; however, insertion mechanisms and types of interaction remain poorly understood. The present study used a new methodology to investigate interactions between OM and the calcite matrix during crystallization processes with humic acid (HA) entrapment. A multimethod approach confirmed that HA is both adsorbed onto the calcite surface and incorporated into the calcite lattice during crystallization. Our results also confirm the log-linear correlation between fluorescence intensity and calcite matrix HA concentration. Fourier transform infrared spectroscopy showed that HA in colloidal conformation is adsorbed onto the calcite surface as a result of the structure of the OH stretching band. We also developed a new method based on synchrotron analysis that uses sulfur as a tracer element for entrapped HA and that localizes the OM electrostatically adsorbed onto the calcite surface. Changes in the sulfur environment, determined using X-ray absorption near-edge structure spectroscopy, indicated more complex insertion mechanisms than simple adsorption of HA during calcite crystallization. Desorption experiments revealed the stability of the OM atomic structure and its layered nature. These results allowed us to draw up a general model of OM insertion in calcite.

Sedimentary structure discrimination with hyperspectral imaging in sediment cores.

Hyperspectral imaging (HSI) is a non-destructive, high-resolution imaging technique that is currently under significant development for analyzing geological areas with remote devices or natural samples in a laboratory. In both cases, the hyperspectral image provides several sedimentary structures that must be separated to temporally and spatially describe the sample. Sediment sequences are composed of successive deposits (strata, homogenite, flood) that are visible depending on sample properties. The classical methods to identify them are time-consuming, have a low spatial resolution (millimeters) and are generally based on naked-eye counting. In this study, we compare several supervised classification algorithms to discriminate sedimentological structures in lake sediments. Instantaneous events in lake sediments are generally linked to extreme geodynamical events (e.g., floods, earthquakes), so their identification and counting are essential to understand long-term fluctuations and improve hazard assessments. Identification and counting are done by reconstructing a chronicle of event layer occurrence, including estimation of deposit thicknesses. Here, we applied two hyperspectral imaging sensors (Visible Near-Infrared, VNIR, 60 µm, 400-1000 nm; Short Wave Infrared, SWIR, 200 µm, 1000-2500 nm) on three sediment cores from different lake systems. We highlight that the SWIR sensor is the optimal one for creating robust classification models with discriminant analyses (prediction accuracies of 0.87-0.98). Indeed, the VNIR sensor is impacted by the surface reliefs and structures that are not in the learning set, which causes mis-classification. These observations are also valid for the combined sensor (VNIR-SWIR) and the RGB images. Several spatial and spectral pre-processing were also compared and enabled one to highlight discriminant information specific to a sample and a sensor. These works show that the combined use of hyperspectral imaging and machine learning improves the characterization of sedimentary structures compared to conventional methods.

High-resolution prediction of organic matter concentration with hyperspectral imaging on a sediment core.

In the case of environmental samples, the use of a chemometrics-based prediction model is highly challenging because of the difficulty in experimentally creating a well-ranged reference sample set. In this study, we present a methodology using short wave infrared hyperspectral imaging to create a partial least squares regression model on a cored sediment sample. It was applied to a sediment core of the well-known Lake Bourget (Western Alps, France) to develop and validate a model for downcore high resolution LOI550 measurements used as a proxy of the organic matter. In lake and marine sediment, the organic matter content is widely used, for example, to reconstruct carbon flux variations through time. Organic matter analysis through routine analysis methods is time- and material-consuming, as well as not spatially resolved. A new instrument based on hyperspectral imaging allows high spatial and spectral resolutions to be acquired all along a sediment core. In this study, we obtain a model characterized by a 0.95 r prediction, with 0.77 wt% of model uncertainty based on 27 relevant wavelengths. The concentration map shows the variation inside each laminae and flood deposit. LOI550 reference values obtained with the loss on ignition are highly correlated to the inc/coh ratio used as a proxy of the organic matter in X-ray fluorescence with a correlation coefficient of 0.81. This ratio is also correlated with the averaged subsampled hyperspectral prediction with a r of 0.65.

DNA from lake sediments reveals long-term ecosystem changes after a biological invasion.

What are the long-term consequences of invasive species? After invasion, how long do ecosystems require to reach a new equilibrium? Answering these questions requires long-term, high-resolution data that are vanishingly rare. We combined the analysis of environmental DNA extracted from a lake sediment core, coprophilous fungi, and sedimentological analyses to reconstruct 600 years of ecosystem dynamics on a sub-Antarctic island and to identify the impact of invasive rabbits. Plant communities remained stable from AD 1400 until the 1940s, when the DNA of invasive rabbits was detected in sediments. Rabbit detection corresponded to abrupt changes of plant communities, with a continuous decline of a dominant plant species. Furthermore, erosion rate abruptly increased with rabbit abundance. Rabbit impacts were very fast and were stronger than the effects of climate change during the 20th century. Lake sediments can allow an integrated temporal analysis of ecosystems, revealing the impact of invasive species over time and improving our understanding of underlying mechanisms.

Therapeutic vaccination with TNF-Kinoid in TNF antagonist-resistant rheumatoid arthritis: a phase II randomized, controlled clinical trial.

OBJECTIVES: Active immunization, or vaccination, with tumor necrosis factor (TNF)-Kinoid (TNF-K) is a novel approach to induce polyclonal anti-TNF antibodies in immune-mediated inflammatory diseases. This study was performed to transfer the proof of concept obtained in mice model of rheumatoid arthritis (RA) into human. We designed a pilot study to demonstrate the feasibility of therapeutic vaccination in RA. METHODS: This was a phase IIa, placebo-controlled, multicenter study in adults with RA who previously experienced secondary failure of TNF antagonists. Patients were immunized intramuscularly with 2 or 3 doses of placebo (n = 10) or 90 (n = 6), 180 (n = 12), or 360 µg TNF-K (n = 12). The primary objective was to identify the best dose and schedule based on anti-TNF antibody titers. Clinical symptoms and safety were assessed during 12 months and solicited reactions for 7 days after each injection. RESULTS: The highest anti-TNF antibody response was detected in patients immunized with 360 µg TNF-K and with 3 injections, although this difference was not significant with all other groups. Similar proportions of patients receiving TNF-K and placebo reported adverse events up to month 12. Serious adverse events were reported by 4 patients treated with TNF-K (13.3%) and 3 treated with placebo (30.0%), all unrelated to treatment. At month 12, DAS28-CRP, tender and swollen joint counts, and HAQ scores decreased significantly more in patients who exhibited anti-TNF antibody response than in patients who did not. CONCLUSIONS: TNF-K therapeutic vaccination induced dose- and schedule-dependent anti-TNF antibodies in RA patients and was well tolerated. Patients who developed anti-TNF antibodies showed a trend toward clinical improvement. Although the most aggressive dose and schedule, i.e. 360 mg dose administered 3 times, did show a strong trend of higher antibody response, further studies are warranted to examine even higher and more frequent doses in order to establish the best conditions for clinical improvement. TRIAL REGISTRATION: ClinicalTrials.gov NCT01040715.

Correction of inner filter effect in mirror coating cells for trace level fluorescence measurements.

The sensitivity of the spectrofluorometric technique can be improved by a factor of about 3.6 using a mirror coating cell. In the case of a large working range, the nonlinear relationship due to the absorbance of solutions between concentration of the analyte of interest and fluorescence intensity (called inner filter effect) must be corrected. This paper suggests a universal inner filter correction equation based on the physical absorbance phenomenon of a mirror coating cell that only depends on the solution absorbance spectra and the cell parameters. These parameters are determined with rhodamine b standard solutions and a simplex method-based mathematical fitting. The methodology has been successfully applied to the correction of classical and synchronous spectra in absorbent media. The partial least squares (PLS) quantification of a mixture of trace levels (approximately 1-10 microg L(-1)) of six polycyclic aromatic hydrocarbons (PAHs) by synchronous fluorescence is possible, even in an absorbent matrix. This simple method allows extension of the analytical field of fluorescence quantification to a large working range in absorbent solutions.

Use of a Plackett-Burman design with multivariate calibration for the analysis of polycyclic aromatic hydrocarbons in micellar media by synchronous fluorescence.

This work describes the use of a multilevel Plackett-Burman design (PB) for the creation of a calibration set for partial least square regression (PLS). The PB calibration set was compared to a collinear analogue by testing these two PLS models for the analysis of six polycyclic aromatic hydrocarbons (PAHs). These compounds were analyzed in micellar media by synchronous fluorescence after determination of the experimental conditions (choice of surfactant, analytical conditions such as deltalambda, step, and scan range). The external validation shows that the collinear set is inappropriate to quantify PAH in real samples, but the PB calibration set affords optimal results.