Evaluation of the efficacy of a portable LIBS system for detection of CWA on surfaces

Laser-induced breakdown spectroscopy (LIBS) is a laser-based optical technique particularly suited for in situ surface analysis. A portable LIBS instrument was tested to detect surface chemical contamination by chemical warfare agents (CWAs). Test of detection of surface contamination was carried out in a toxlab facility with four CWAs, sarin (GB), lewisite (L1), mustard gas (HD), and VX, which were deposited on different substrates, wood, concrete, military green paint, gloves, and ceramic. The CWAs were detected by means of the detection of atomic markers (As, P, F, Cl, and S). The LIBS instrument can give a direct response in terms of detection thanks to an integrated interface for non-expert users or so called end-users. We have evaluated the capability of automatic detection of the selected CWAs. The sensitivity of our portable LIBS instrument was confirmed for the detection of a CWA at surface concentrations above 15 μg/cm². The simultaneous detection of two markers may lead to a decrease of the number of false positive.     

Spatial and temporal organization of benthic macroinvertebrate communities in Lake Chany,Western Siberia

Communities of benthic macroinvertebrates in drainless Lake Chany, the largest lake in Western Siberia, have been analyzed to estimate the effects of basic abiotic ecological factors (hydrophysical and hydrochemical parameters of water and the type of bottom ground) on their composition, structure, and dynamics. It has been shown that the level of development of these communities depends mainly on the water regime of the lake and also on the type of bottom ground, lake depth, and water mineral content.     

Characteristics of stone moroko population dynamics at different stages of naturalization in lake- and steam-type Dnieper reservoirs

The probable source of stone moroko, Pseudorasbora parva (Temminck & Schlegel, 1846), populations in lake- and stream-type Dnieper reservoirs was revealed. The dynamics and specific growth rates of these populations over 20 years were analyzed. The dynamic phase portrait method was used to determine the timing of stages in the process of invader naturalization and the periods when its populations were in equilibrium. The potential growth rates of P. parva populations in the Kremenchug and Dneprodzerzhinsk reservoirs were estimated.     

Common buzzards (Buteo buteo) bio-indicators of heavy metals pollution in Sicily (Italy)

The aim of this study was to evaluate the accumulation of toxic (As, Cd and Pb) and essential (Cu, Mn and Zn) metals in samples (feathers, liver, kidney, lung, intestine and muscle) of common buzzards (Buteo buteo) from Sicily, used as bio-indicators for monitoring environmental metals pollution. All samples of buzzards were collected at the “Recovery Center of Wild Fauna” of Palermo, through the Zooprophilactic Institute. The quantitative determinations of metals were carried out using an atomic absorbtion spectrophotometer (AAS). The results obtained showed the presence of metals in all samples analyzed. For toxic metals the highest levels of Pb and As were found in liver and those of Cd in kidney; for essential metals Zn levels were higher than Cu and Mn in all tissues analyzed. Significant differences are observed in metal levels between female and male and juvenile and adult bird samples.Highest metal levels found in liver, kidney and muscle can be considered indicative of chronic exposure to metals while the presence of metals in feathers can be consequential to storing and elimination processes. The results obtained suggest that common buzzards (Buteo buteo) may be very useful as bio-indicators for monitoring environmental pollution.     

Impact of European legislation on marketed pesticides — A view from the standpoint of health impact assessment studies

The very significant impact of European legislation (Directive 91/414/EEC) on the authorization of plant protection products is reviewed herein, which has resulted in withdrawal of 704 active substances (AS) out of 889 assessed so far. The list of currently approved 276 AS includes 194 AS “existing” in the market before 1993 and 82 “new” AS introduced during the last 15 years. Results of toxicity characterization of the approved AS are also summarized, utilizing several well-known databases. Although significant data gaps exist for a rather large part of the approved AS, it is found that 84 AS are positive for at least one health effect (after chronic and/or acute exposure) including carcinogenicity, reproductive and neuro-developmental disorders, as well as endocrine disruption. The toxicity characterization results of this study are compared to those of recent assessments by other organizations (KemI, the Swedish Chemicals Agency, and the Pesticide Safety Directorate of the UK), where interpretation and use is made of AS “cut-off” criteria foreseen in new EU legislation. These studies report a comparatively smaller AS number with positive toxicity characterization. The possibility of some additional AS withdrawal in the near future, combined with the rather small rate of new AS introduction (approx. 5 per year) suggest that the list of approved AS over the next 10–15 years may not change very drastically. Consideration of the above trends is necessary and instructive in evaluating results of existing health impact assessment (HIA) studies, as well as in planning new ones. Due to the very drastic change in the number and type of marketed AS, that took place within the past 8–9 years, it is suggested that new HIA studies (based on epidemiological data after year 2000) should focus on a rather short time frame and, therefore, on appropriate cohort groups, e.g. young children. For the same reason, results of epidemiological studies of the past (involving banned AS) should be carefully interpreted and used with caution.     

Residential runoff as a source of pyrethroid pesticides to urban creeks

Pyrethroid pesticides occur in urban creek sediments at concentrations acutely toxic to sensitive aquatic life. To better understand the source of these residues, runoff from residential neighborhoods around Sacramento, California was monitored over the course of a year. Pyrethroids were present in every sample. Bifenthrin, found at up to 73 ng/L in the water and 1211 ng/g on suspended sediment, was the pyrethroid of greatest toxicological concern, with cypermethrin and cyfluthrin of secondary concern. The bifenthrin could have originated either from use by consumers or professional pest controllers, though the seasonal pattern of discharge from the drain was more consistent with professional use as the dominant source. Stormwater runoff was more important than dry season irrigation runoff in transporting pyrethroids to urban creeks. A single intense storm was capable of discharging as much bifenthrin to an urban creek in 3 h as that discharged over 6 months of irrigation runoff.     

A study of the total atmospheric sulfur dioxide load using ground-based measurements and the satellite derived Sulfur Dioxide Index

We present characteristics of the sulfur dioxide (SO₂) loading over Thessaloniki, Greece, and seven other selected sites around the world using SO₂ total column measurements from Brewer spectrophotometers together with satellite estimates of the Version 8 TOMS Sulfur Dioxide Index (SOI) over the same locations, retrieved from Nimbus 7 TOMS (1979–1993), Earth Probe TOMS (1996–2003) and OMI/Aura (2004–2006). Traditionally, the SOI has been used to quantify the SO₂ quantities emitted during great volcanic eruptions. Here, we investigate whether the SOI can give an indication of the total SO₂ load for areas and periods away from eruptive volcanic activity by studying its relative changes as a correlative measure to the SO₂ total column. We examined time series from Thessaloniki and another seven urban and non-urban stations, five in the European Union (Arosa, De Bilt, Hohenpeissenberg, Madrid, Rome) and two in India (Kodaikanal, New Delhi). Based on the Brewer data, Thessaloniki shows high SO₂ total columns for a European Union city but values are still low if compared to highly affected regions like those in India. For the time period 1983–2006 the SO₂ levels above Thessaloniki have generally decreased with a rate of 0.028 Dobson Units (DU) per annum, presumably due to the European Union's strict sulfur control policies. The seasonal variability of the SO₂ total column exhibits a double peak structure with two maxima, one during winter and the second during summer. The winter peak can be attributed to central heating while the summer peak is due to synoptic transport from sources west of the city and sources in the north of Greece. A moderate correlation was found between the seasonal levels of Brewer total SO₂ and SOI for Thessaloniki, Greece (R = 0.710–0.763) and Madrid, Spain (R = 0.691) which shows that under specific conditions the SOI might act as an indicator of the SO₂ total load.     

A validated 2-D diffusion–advection model for prediction of drift from ground boom sprayers

Correct field drift prediction is a key element in environmental risk assessment of spraying applications. A reduced order drift prediction model based on the diffusion–advection equation is presented. It allows fast assessment of the drift potential of specific ground boom applications under specific environmental wind conditions that obey the logarithmic wind profile. The model was calibrated based on simulations with a validated Computational Fluid Dynamics (CFD) model. Validation of both models against 38 carefully conducted field experiments is successfully performed for distances up to 20 m from the field edge, for spraying on flat pasture land. The reduced order model succeeded in correct drift predictions for different nozzle types, wind velocities, boom heights and spray pressures. It used 4 parameters representing the physical aspects of the drift cloud; the height of the cloud at the field edge, the mass flux crossing the field edge, the settling velocity of the droplets and the turbulence. For the parameter set and range considered, it is demonstrated for the first time that the effect of the droplet diameter distribution of the different nozzle types on the amount of deposition spray drift can be evaluated by a single parameter, i.e., the volume fraction of droplets with a diameter smaller than 191 μm. The reduced order model can be solved more than 4 orders of magnitude faster than the comprehensive CFD model.     

Influence of air mass source region on nanoparticle events and hygroscopicity in central Virginia,U.S.

During autumn, 2006, variation in the frequency of aerosol nucleation events, as inferred from nanoparticle growth events, and associated hygroscopicity were investigated as a function of air mass transport history at a mixed deciduous forest in central Virginia, U.S. Above-canopy size distributions of aerosols between 0.012 and 0.700 μm diameter, size-resolved particle hygroscopicity at eight dry diameters between 0.012 and 0.400 μm, and cloud condensation nuclei (CCN) activity were characterized. Air mass back trajectories were clustered to identify source regions. Growth events were most frequent in fast-moving air masses (mean = 9 m s^?1) that originated over the north central U.S. Under these flow regimes, mean values for preexisting sub-μm aerosol number concentrations (4700 cm^?3), corresponding surface area (142 μm² cm^?3), air temperature (6.2 °C), and relative humidity (RH, 49.4%) were relatively low compared to other regimes. Under stagnant flow conditions (mean = 3 m s^?1), mean number concentrations were higher (>6000 cm^?3) and size fractions <0.1 μm diameter exhibited enhanced hygroscopicity compared to other source regions. These results indicate that precursors emitted into relatively clean, cold, and dry air transported over the southeastern U.S. reacted to form condensable intermediates that subsequently produced new aerosols via nucleation and growth. This pathway was an important source for CCN. During events in October, nanoparticles were produced in greater numbers and grew more rapidly compared to November and December.     

Assessing spatial variability of SO2 field as detected by an air quality network using Self-Organizing Maps,cluster, and Principal Component Analysis

In Bilbao (Spain), an air quality network measures sulphur dioxide levels at 4 locations. The objective of this paper is to develop a practical methodology to identify redundant sensors and evaluate a network's capability to correctly follow and represent SO₂ fields in Bilbao, in the frame of a continuous network optimization process.The methodology is developed and tested at this particular location, but it is general enough to be useable at other places as well, since it is not tied neither to the particular geographical characteristics of the place nor to the phenomenology of the air quality over the area.To assess the spatial variability of SO₂ measured at 4 locations in the area, three different techniques have been used: Self-Organizing Maps (SOMs), cluster analysis (CA) and Principal Component Analysis (PCA). The results show that the three techniques yield the same results, but the information obtained via PCA can be helpful not only for that purpose but also to throw light on the major mechanisms involved. This might be used in future network optimization stages. The main advantage of cluster analysis and SOMs is that they provide readily interpretable results. All the calculations have been carried out using the freely available software R.