Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

Initial effects of light armored vehicle use on grassland vegetation at Fort Lewis, Washington

Sustainable use of military training lands requires understanding and prediction of the effects of military vehicles on vegetation. We examined the initial impacts of an 8-wheeled, light armored vehicle (LAV) on grassland vegetation at Fort Lewis, Washington. The LAV drove replicate spiral paths at two starting velocities, 10.3 and 5.1 m s(-1). The disturbed width (width of ground impacted by the tires) increased as turning radius decreased, but was unaffected by vehicle velocity. An inverse-exponential model predicted disturbed width (r(2)=0.68) at all turning radii for both velocities combined. In low-velocity spirals, and for straight tracking (turning radius>40 m) and moderate turns (radius 20-40 m) in high-velocity spirals, all vegetation damage was imprint (plants flattened by wheels). During sharp (radius <20 m), high-velocity turns, most or all of the disturbed width was scraped free of surface vegetation and soil, which was piled to the outside of each tire track. Total plant cover (all species) was not affected by track curvature in low-velocity spirals, but decreased in the order straight tracking>moderate turns>sharp turns in high-velocity spirals. In low-velocity spirals, post-tracking cover of several plant growth forms (non-native species, perennial species, sod-forming grasses) was similar to pre-tracking cover, but in high-velocity spirals, post-tracking cover of these growth forms decreased in the order straight > or =moderate=sharp. Cover of native species and forbs decreased more in high- than in low-velocity spirals, but was unaffected by curvature. Pre- and post-tracking cover of annual species, bunchgrasses, and shrubs was < or =3%. The most severe vegetation damage caused by operation of wheeled LAVs on grasslands is associated with sharp, high-velocity turns.     

Monitoring and assessing of landscape heterogeneity at different scales

In numerous studies, spatial and spectral aggregations of pixel information using average values from imaging spectrometer data are suggested to derive spectral indices and the subsequent vegetation parameters that are derived from these. Currently, there are very few empirical studies that use hyperspectral data, to support the hypothesis for deriving land surface variables from different spectral and spatial scales. In the study at hand, for the first time ever, investigations were carried out on fundamental scaling issues using specific experimental test flights with a hyperspectral sensor to investigate how vegetation patterns change as an effect of (1) different spatial resolutions, (2) different spectral resolutions, (3) different spatial and spectral resolutions as well as (4) different spatial and spectral resolutions of originally recorded hyperspectral image data compared to spatial and spectral up- and downscaled image data. For these experiments, the hyperspectral sensor AISA-EAGLE/HAWK (DUAL) was mounted on an aircraft to collect spectral signatures over a very short time sequence of a particular day. In the first experiment, reflectance measurements were collected at three different spatial resolutions ranging from 1 to 3 m over a 2-h period in 1 day. In the second experiment, different spectral image data and different additional spatial data were collected over a 1-h period on a particular day from the same test area. The differently recorded hyperspectral data were then spatially and spectrally rescaled to synthesize different up- and down-rescaled images. The normalised difference vegetation index (NDVI) was determined from all image data. The NDVI heterogeneity of all images was compared based on methods of variography. The results showed that (a) the spatial NDVI patterns of up- and downscaled data do not correspond with the un-scaled image data, (b) only small differences were found between NDVI patterns determined from data recorded and resampled at different spectral resolutions and (c) the overall conclusion from the tests carried out is that the spatial resolution is more important in determining heterogeneity by means of NDVI than the depth of the spectral data. The implications behind these findings are that we need to exercise caution when interpreting and combining spatial structures and spectral indices derived from satellite images with differently recorded geometric resolutions.     

Inorganic and organic contaminants in Alaskan shorebird eggs

Many shorebird populations throughout North America are thought to be declining, with potential causes attributed to habitat loss and fragmentation, reduced prey availability, increased predation, human disturbance, and increased exposure to environmental pollutants. Shorebirds may be particularly vulnerable to contaminant exposure throughout their life cycle, as they forage primarily on invertebrates in wetlands, where many contaminants accumulate disproportionately in the sediments. Therefore, it is important to document and monitor shorebird populations thought to be at risk and assess the role that environmental contaminants may have on population declines. To investigate potential threats and provide baseline data on shorebird contaminant levels in Alaskan shorebirds, contaminant concentrations were evaluated in shorebird eggs from 16 species residing in seven geographic distinct regions of Alaska. Similar to previous studies, low levels of most inorganic and organic contaminants were found, although concentrations of several inorganic and organic contaminants were higher than those of previous studies. For example, elevated strontium levels were observed in several species, especially black oystercatcher (Haematopus bachmani) sampled in Prince William Sound, Alaska. Additionally, contaminant concentrations varied among species, with significantly higher concentrations of inorganic contaminants found in eggs of pectoral sandpiper (Calidris melanotos), semipalmated sandpiper (Calidris pusilla), black oystercatcher, and bar-tailed godwit (Limosa lapponica). Similarly, significantly higher concentrations of some organic contaminants were found in the eggs of American golden plover (Pluvialis dominica), black-bellied plover (Pluvialis squatarola), pacific golden plover (Pluvialis fulva), bar-tailed godwit, and semipalmated sandpiper. Despite these elevated levels, current concentrations of contaminants in shorebird eggs suggest that breeding environments are relatively free of most contaminants and that contaminant concentrations are below levels (except potentially strontium) that would likely affect the survival of individuals and consequently regulate the species at the population level.     

Ecosystem classification for EU habitat distribution assessment in sandy coastal environments: An application in central Italy

Many recent developments in coastal science have gone against the demands of European Union legislation. Coastal dune systems which cover small areas of the earth can host a high level of biodiversity. However, human pressure on coastal zones around the world has increased dramatically in the last 50 years. In addition to direct habitat loss, the rapid extinction of many species that are unique to these systems can be attributed to landscape deterioration through the lack of appropriate management. In this paper, we propose to use of an ecosystem classification technique that integrates potential natural vegetation distribution as a reference framework for coastal dune EU Habitats (92/43) distribution analysis and assessment. As an example, the present study analyses the EU Habitats distribution within a hierarchical ecosystem classification of the coastal dune systems of central Italy. In total, 24 land elements belonging to 8 land units, 5 land facets, 2 land systems and 2 land regions were identified for the coastal dunes of central Italy, based on diagnostic land attributes. In central Italy, coastal dune environments including all the beach area, mobile dunes and all the fixed-dune land elements contain or could potentially hold at least one EU habitat of interest. Almost all dune slack transitions present the potentiality for the spontaneous development of EU woodlands of interest. The precise information concerning these ecosystems distribution and ecological relationships that this method produces, makes it very effective in Natura 2000 European network assessment. This hierarchical ecosystem classification method facilitates the identification of areas to be surveyed and eventually bound, under the implementation of EU Habitat directive (92/43) including areas with highly disturbed coastal dune ecosystems.     

A new multiscale approach for monitoring vegetation using remote sensing-based indicators in laboratory, field, and landscape

Remote sensing is an important tool for studying patterns in surface processes on different spatiotemporal scales. However, differences in the spatiospectral and temporal resolution of remote sensing data as well as sensor-specific surveying characteristics very often hinder comparative analyses and effective up- and downscaling analyses. This paper presents a new methodical framework for combining hyperspectral remote sensing data on different spatial and temporal scales. We demonstrate the potential of using the “One Sensor at Different Scales” (OSADIS) approach for the laboratory (plot), field (local), and landscape (regional) scales. By implementing the OSADIS approach, we are able (1) to develop suitable stress-controlled vegetation indices for selected variables such as the Leaf Area Index (LAI), chlorophyll, photosynthesis, water content, nutrient content, etc. over a whole vegetation period. Focused laboratory monitoring can help to document additive and counteractive factors and processes of the vegetation and to correctly interpret their spectral response; (2) to transfer the models obtained to the landscape level; (3) to record imaging hyperspectral information on different spatial scales, achieving a true comparison of the structure and process results; (4) to minimize existing errors from geometrical, spectral, and temporal effects due to sensor- and time-specific differences; and (5) to carry out a realistic top- and downscaling by determining scale-dependent correction factors and transfer functions. The first results of OSADIS experiments are provided by controlled whole vegetation experiments on barley under water stress on the plot scale to model LAI using the vegetation indices Normalized Difference Vegetation Index (NDVI) and green NDVI (GNDVI). The regression model ascertained from imaging hyperspectral AISA-EAGLE/HAWK (DUAL) data was used to model LAI. This was done by using the vegetation index GNDVI with an R ² of 0.83, which was transferred to airborne hyperspectral data on the local and regional scales. For this purpose, hyperspectral imagery was collected at three altitudes over a land cover gradient of 25 km within a timeframe of a few minutes, yielding a spatial resolution from 1 to 3 m. For all recorded spatial scales, both the LAI and the NDVI were determined. The spatial properties of LAI and NDVI of all recorded hyperspectral images were compared using semivariance metrics derived from the variogram. The first results show spatial differences in the heterogeneity of LAI and NDVI from 1 to 3 m with the recorded hyperspectral data. That means that differently recorded data on different scales might not sufficiently maintain the spatial properties of high spatial resolution hyperspectral images.     

The OECD validation program of the H295R steroidogenesis assay: Phase 3. Final inter-laboratory validation study

Background, goals, and scope

In response to increasing concerns regarding the potential of chemicals to interact with the endocrine system of humans and wildlife, various national and international programs have been initiated with the aim to develop new guidelines for the screening and testing of these chemicals in vertebrates. Here, we report on the validation of an in vitro assay, the H295R steroidogenesis assay, to detect chemicals with the potential to inhibit or induce the production of the sex steroid hormones testosterone (T) and 17??-estradiol (E2) in preparation for the development of an Organization for Economic Cooperation and Development (OECD) test guideline.

Methods

A previously optimized and pre-validated protocol was used to assess the potential of 28 chemicals of diverse structures and properties to validate the H295R steroidogenesis assay. These chemicals are comprised of known endocrine-active chemicals and ??negative?? chemicals that were not expected to have effects on the targeted endpoints, as well as a number of test chemicals with unknown modes of action at the level of the steroidogenic pathway. A total of seven laboratories from seven countries participated in this effort. In addition to effects on hormone production, confounding factors, such as cell viability and possible direct interference of test substances with antibody-based hormone detection assays, were assessed. Prior to and during the conduct of exposure experiments, each laboratory had to demonstrate that they were able to conduct the assay within the margin of predefined performance criteria.

Results

With a few exceptions, all laboratories met the key quality performance parameters, and only 2% and 7% of all experiments for T and E2, respectively, were excluded due to exceedance of these parameters. Of the 28 chemicals analyzed, 13 and 14 tested affected production of T and E2, respectively, while 11 and 8 did not result in significant effects on T and E2 production, respectively. Four and six chemicals produced ambiguous results for effects on T and E2 production, respectively. However, four of these cases each for T and E2 were associated with only one laboratory after a personnel change occurred. Significant interference of test chemicals with some of the antibody-based hormone detection systems occurred for four chemicals. Only one of these chemicals, however, significantly affected the ability of the detection system to categorize the chemical as affecting E2 or T production.

Discussion and conclusions

With one exception, the H295R steroidogenesis assay protocol successfully identified the majority of chemicals with known and unknown modes of interaction as inducers or inhibitors of T and E2 production. Thus it can be considered a reliable screen for chemicals that can alter the production of sex steroid hormones. One of the remaining limitations associated with the H295R steroidogenesis assay protocol is the relatively small basal production of E2 and its effect on quantifying the decreased production of this hormone with regard to the identification of weak inhibitors. An initial comparison of the data produced in this study with those from in vivo studies from the literature demonstrated the potential of the H295R steroidogenesis assay to identify chemicals affecting hormone homeostasis in whole organisms. Particularly promising was the lack of any false negatives during the validation and the very low number of false positives (1 out of 28 chemicals for each T and E2).

Perspectives

Based on the results obtained during this validation study and the accordingly revised test protocols, an OECD draft test guideline was developed and submitted to the OECD working group of the national coordinators of the test guidelines program (WNT) for comments in December 2009.     

Dependence of Ozone Biomonitoring on Meteorological Conditions of Different Sites in Catalonia (N.E. Spain)

Evaluation of visual symptoms of ozone damage was conducted in the network of bioindicator rural stations of Catalonia (NE Spain) every 14 days from May to October. Damage rates of ozone (and consequently, ozone biomonitoring capacity of bioindicators) were found to vary highly in time and space depending on the local environmental and meteorological conditions. Lower ozone damage to foliage was produced when meteorological conditions favour stomata resistance. Modulatory effects of meteorological conditions need to be considered in biomonitoring and when modeling plant ozone doses and damage.     

The impact of semiconductor, electronics and optoelectronic industries on downstream perfluorinated chemical contamination in Taiwanese rivers

This study provides the first evidence on the influence of the semiconductor and electronics industries on perfluorinated chemicals (PFCs) contamination in receiving rivers. We have quantified ten PFCs, including perfluoroalkyl sulfonates (PFASs: PFBS, PFHxS, PFOS) and perfluoroalkyl carboxylates (PFCAs: PFHxA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA) in semiconductor, electronic, and optoelectronic industrial wastewaters and their receiving water bodies (Taiwan's Keya, Touchien, and Xiaoli rivers). PFOS was found to be the major constituent in semiconductor wastewaters (up to 0.13 mg/L). However, different PFC distributions were found in electronics plant wastewaters; PFOA was the most significant PFC, contributing on average 72% to the effluent water samples, followed by PFOS (16%) and PFDA (9%). The distribution of PFCs in the receiving rivers was greatly impacted by industrial sources. PFOS, PFOA and PFDA were predominant and prevalent in all the river samples, with PFOS detected at the highest concentrations (up to 5.4 μg/L).     

Rapid determination of residues of pesticides in honey by µGC-ECD and GC-MS/MS: Method validation and estimation of measurement uncertainty according to document No. SANCO/12571/2013

A simple and straightforward method for simultaneous determination of residues of 13 pesticides in honey samples (acrinathrin, bifenthrin, bromopropylate, cyhalothrin-lambda, cypermethrin, chlorfenvinphos, chlorpyrifos, coumaphos, deltamethrin, fluvalinate-tau, malathion, permethrin and tetradifon) from different pesticide classes has been developed and validated. The analytical method provides dissolution of honey in water and an extraction of pesticide residues by n-Hexane followed by clean-up on a Florisil SPE column. The extract was evaporated and taken up by a solution of an injection internal standard (I-IS), ethion, and finally analyzed by capillary gas chromatography with electron capture detection (GC-µECD). Identification for qualitative purpose was conducted by gas chromatography with triple quadrupole mass spectrometer (GC-MS/MS). A matrix-matched calibration curve was performed for quantitative purposes by plotting the area ratio (analyte/I-IS) against concentration using a GC-µECD instrument. According to document No. SANCO/12571/2013, the method was validated by testing the following parameters: linearity, matrix effect, specificity, precision, trueness (bias) and measurement uncertainty. The analytical process was validated analyzing blank honey samples spiked at levels equal to and greater than 0.010 mg/kg (limit of quantification). All parameters were satisfactorily compared with the values established by document No. SANCO/12571/2013. The analytical performance was verified by participating in eight multi-residue proficiency tests organized by BIPEA, obtaining satisfactory z-scores in all 70 determinations. Measurement uncertainty was estimated according to the top-down approaches described in Appendix C of the SANCO document using the within-laboratory reproducibility relative standard deviation combined with laboratory bias using the proficiency test data.