Effects of humidity and filter material on diffusive sampling of isocyanates using reagent-coated filters

Diffusive sampling of methyl isocyanate (MIC) on 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ)-coated glass fibre (GF) filters is strongly affected by high relative humidity (RH) conditions. It is shown that the humidity interference is a physical phenomenon, based on displacement of reagent from the filter surface. In this paper, this drawback has been overcome by changing the filter material to the less polar polystyrene divinyl benzene (SDB). A series of experiments was performed to compare the analyte uptake on the two filter materials for different sampling periods and analyte concentrations at both low and high RH conditions. Additionally, the materials were investigated as well for passive sampling of ethyl (EIC) and phenyl isocyanate (PhIC) with NBDPZ and 1-(2-methoxyphenyl) piperazine (2-MP) as an alternative derivatising agent. Using 2-MP, the mean GF/SDB response ratios were determined to be 1.02 for MIC (RSD: 6.1%) and 1.03 for EIC (RSD: 6.8%), whereas PhIC could only be determined on SDB filters. Using NBDPZ as reagent, the negative influence of high humidity disappeared when SDB filters were used instead of GF filters. Even at low RH conditions, sampling with SDB material generally resulted in a higher analyte uptake than with GF filters. The GF/SDB response ratios were independent of sampling time or analyte concentration and were determined to be 0.70 (RSD: 4.7%) for MIC, 0.84 (RSD: 4.5%) for EIC and 0.95 (RSD 5.4%) for PhIC, meaning that the NBDPZ diffusive sampler based on SDB can be used at all humidity conditions without any restrictions.     

Sequentielle Schwermetallextraktion aus Staubniederschlägen und Stra\ensedimenten

For the application of our method for the sequential extraction of heavy metals from microsamples presented in part 1 (“Sequentielle Schwermetallextraktion von Mikroproben” — “Sequential Extraction of Heavy Metals from Micro Samples”) an investigation was carried out to evaluate airborne dust fallout and street sediments at two urban sites where different heavy metal immission rates occur due to traffic influence. In the street sediments the total concentrations of zinc, copper and lead was three to fivefold higher in the silt and clay fraction (< 63 μm) than in the particle size fraction (< 1,12 mm), but showed nearly the same mobilisation behaviour. The dust samples showed equal mobilisation behaviour as the street sediments for copper and lead, while zinc was considerably more mobile in the dust samples: In extraction steps I–IV (I: mobile fraction; II: easily deliverable fraction; III: fraction bound to manganese oxides; IV: fraction bound organic to matter) zinc, copper and lead in street sediments, as well as copper and lead in dust samples, were dissolved to 40–70%, whereas about 80% of zinc in the dust samples was already dissolved in extraction step I.     

Citizen-Science and Participatory Research as a Means to Improve Stakeholder Engagement in Resource Management: A Case Study of Vietnamese American Fishers on the US Gulf Coast

Environmental Management - This study examines the engagement of Vietnamese American commercial fisheries stakeholders in the US Gulf Coast with state and federal agencies and the role that citizen...     

Aerosol trace metals,particle morphology and total gaseous mercury in the atmosphere of Oxford,UK

An investigation of atmospheric trace metals was conducted in Oxford, UK, a small city ～60 miles northwest of London, in 2007 and 2008. Concentrations of Sr, Mo, Cd, Pb, V, Cr, Mn, Fe, Co, Ni, Cu and Zn in aerosol were measured in bulk and size segregated samples. In addition, total gaseous mercury (TGM) concentrations were monitored semi-continuously by cold vapour-atomic fluorescence spectroscopy. Metal concentrations in Oxford were intermediate between previously reported levels of UK rural and urban areas for most metals studied and levels of Cd, Ni and Pb were within European guidelines. Metal concentrations appeared to be influenced by higher traffic volume on a timescale of hours. The influence of traffic on the aerosols was also suggested by the observation of carbonaceous particles via scanning electron microscopy (SEM). Air mass back trajectories suggest air masses arriving in Oxford from London and mainland Europe contained the highest metal concentrations. Aerosol samples collected over Bonfire Weekend, a period of intense firework use and lighting of bonfires in the UK, showed metal concentrations 6–46 times higher than at other times. Strontium, a tracer of firework release, was present at higher concentrations and showed a change in its size distribution from the coarse to fine mode over Bonfire Weekend. The presence of an abundance of spherical Sr particles was also confirmed in SEM images. The average TGM concentration in Oxford was 3.17 ng m^?3 (st. dev. 1.59) with values recorded between 1.32 and 23.2 ng m^?3. This is a higher average value than reported from nearby rural locations, although during periods when air was arriving from the west, similar concentrations to these rural areas were seen in Oxford. Comparison to meteorological data suggests that TGM in Oxford's air is highest when wind is arriving from the east/southeast. This may be due to emissions from London/mainland Europe with a possible contribution from emissions from a local crematorium situated 4 miles east of the sampling site. A diurnal pattern was also observed in the TGM data with a minimum concentration during the day when mercury may have been diluted by thermal mixing of the atmospheric boundary layer. Additionally, this diurnal pattern may reflect variations in a local source of TGM.     

Determination of lindane leachability in soil-biosolid systems and its bioavailability in wheat plants

The leachability of lindane from different biosolid amended soils was determined and compared to its bioavailability. Sand, soil, and a mixture of soil-sand (1:1 w/w) were spiked with lindane, blended with different amounts of biosolids, and subjected to a leaching process with water that lasted for 1-28 d. This procedure is in accordance with ISO/TS 21268-1: 2007. After these batch tests, lindane was extracted from the leachates using three different solvent-free microextraction techniques, including solid phase microextraction (SPME), stir-bar sorptive extraction (SBSE), and silicone rod extraction (SRE). The amount of lindane was determined with thermal desorption and gas chromatography coupled to mass spectrometry (GC-MS). The efficiencies of the three microextraction techniques were statistically different, and the efficiency could be related to the amount of polydimethylsiloxane (PDMS) in each extraction device. However, all of the techniques provide data that shows that the leachability of lindane is dependent on the amount of organic matter contained in the matrix.The results of the lindane leachability assay were compared to the bioavailability of lindane, which was determined by measuring the amount of lindane that accumulated in the roots of wheat plants grown in similar soil-biosolid systems.It was confirmed that the amount of organic matter in the matrix is a determining factor for lindane immobilization. The presence of biosolids decreases the mobility of lindane in all of the systems under study. Similarly, increasing biosolid concentrations in the soil significantly decreased the bioavailability of lindane and, consequently, plant absorption.The good correlation (R² = 0.997) between the leachability of lindane from the matrix and plant absorption of lindane indicates that the proposed biomimetic methodology can predict the bioavailability of lindane in a time period as short as 7 d.The results of this work confirm that amending contaminated soils with biosolids is beneficial for immobilizing lindane and helps prevent the percolation of lindane through the soil profile and into groundwater.     

Truncated Lévy flights and agenda-based mobility are useful for the assessment of personal human exposure

Receptor-oriented approaches can assess the individual-specific exposure to air pollution. In such an individual-based model we analyse the impact of human mobility to the personal exposure that is perceived by individuals simulated in an exemplified urban area. The mobility models comprise random walk (reference point mobility, RPM), truncated Lévy flights (TLF), and agenda-based walk (RPMA). We describe and review the general concepts and provide an inter-comparison of these concepts. Stationary and ergodic behaviour are explained and applied as well as performance criteria for a comparative evaluation of the investigated algorithms. We find that none of the studied algorithm results in purely random trajectories. TLF and RPMA prove to be suitable for human mobility modelling, because they provide conditions for very individual-specific trajectories and exposure. Suggesting these models we demonstrate the plausibility of their results for exposure to air-borne benzene and the combined exposure to benzene and nonane.     

Occurrence of psychoactive compounds and their metabolites in groundwater downgradient of a decommissioned sewage farm in Berlin (Germany)

Purpose

Psychoactive compounds??meprobamate, pyrithyldione, primidone, and its metabolites, phenobarbital, and phenylethylmalonamide??were detected in groundwater within the catchment area of a drinking water treatment plant located downgradient of a former sewage farm in Berlin, Germany. The aim of this study was to investigate the distribution of the psychoactive compounds in anoxic groundwater and to assess the risk of drinking water contamination. Groundwater age was determined to achieve a better understanding of present hydrogeological conditions.

Methods

A large number of observation and production wells were sampled. Samples were analyzed using solid-phase extraction and ultrahigh-performance liquid chromatography?Ctandem mass spectrometry. Groundwater age was estimated using the helium?Ctritium (³He?C³H) dating method.

Results

Concentrations of psychoactive compounds up to 1???g/L were encountered in the contamination plume. Generally, concentrations of phenobarbital and meprobamate were the highest. Elevated concentrations of the analytes were also detected in raw water from abstraction wells located approximately 2.5?km downgradient of the former sewage farm. Concentrations in the final drinking water were below the limit of quantification owing to dilution. The age of shallow groundwater samples ranged from years to a decade, whereas groundwater was up to four decades old at 40?m below ground. Concentrations of the compounds increased with groundwater age.

Conclusions

Elevated concentrations of psychoactive drugs indicate a strong persistence of these compounds in the environment under anoxic aquifer conditions. Results suggest that the heritage of sewage irrigation will affect raw water quality in the area for decades. Therefore, further monitoring of raw and final drinking water is recommended to ensure that contaminant concentrations remain below the health-based precautionary value.     

Degradation of deicing chemicals affects the natural redox system in airfield soils

During winter operations at airports, large amounts of organic deicing chemicals (DIC) accumulate beside the runways and infiltrate into the soil during spring. To study the transport and degradation of DIC in the unsaturated zone, eight undisturbed soil cores were retrieved at Oslo airport, Norway, and installed as lysimeters at a nearby field site. Before snowmelt in 2010 and 2011, snow amended with a mix of the DICs propylene glycol (PG) and formate as well as bromide as conservative tracer was applied. Water samples were collected and analyzed until summer 2012. Water flow and solute transport varied considerably among the lysimeters but also temporally between 2010 and 2011. High infiltration rates during snowmelt resulted in the discharge of up to 51 and 82 % PG in 2010 and 2011, respectively. The discharge of formate remained comparatively low, indicating its favored degradation even at freezing temperatures compared with PG. Manganese (Mn) and iron (Fe) were observed in the drainage in autumn owing to the anaerobic degradation of residual PG during summer. Our findings suggest that upper boundary conditions, i.e., snow cover and infiltration rate, and the extent of preferential flowpaths, control water flow and solute transport of bromide and PG during snowmelt. PG may therefore locally reach deeper soil regions where it may pose a risk for groundwater. In the long term, the use of DIC furthermore causes the depletion of potential electron acceptors and the transport of considerable amounts of Fe and Mn. To avoid an overload of the unsaturated zone with DIC and to maintain the natural redox system, the development of suitable remediation techniques is required.     

Electrical resistivity tomography as monitoring tool for unsaturated zone transport: an example of preferential transport of deicing chemicals

Non-invasive spatially resolved monitoring techniques may hold the key to observe heterogeneous flow and transport behavior of contaminants in soils. In this study, time-lapse electrical resistivity tomography (ERT) was employed during an infiltration experiment with deicing chemical in a small field lysimeter. Deicing chemicals like potassium formate, which frequently impact soils on airport sites, were infiltrated during snow melt. Chemical composition of seepage water and the electrical response was recorded over the spring period 2010. Time-lapse electrical resistivity tomographs are able to show the infiltration of the melt water loaded with ionic constituents of deicing chemicals and their degradation product hydrogen carbonate. The tomographs indicate early breakthrough behavior in parts of the profile. Groundtruthing with pore fluid conductivity and water content variations shows disagreement between expected and observed bulk conductivity. This was attributed to the different sampling volume of traditional methods and ERT due to a considerable fraction of immobile water in the soil. The results show that ERT can be used as a soil monitoring tool on airport sites if assisted by common soil monitoring techniques.     

Zooplankton growth rates: the influence of size and resources in tropical marine copepodites

Growth rates were determined for copepodites of the genera: Acartia, Centropages, Corycaeus, Oithona, Paracalanus, Parvocalanus and Temora in nearshore waters of Jamaica from in situ microcosm incubations. At these high local temperatures (∼28 °C), total copepodite development time was as short as 4 to 5 d. Mean instantaneous growth rates (g) ranged from as high as 1.2 d⁻¹ to as low as 0.1 d⁻¹. In general, cyclopoid copepods appeared to grow more slowly than calanoids of the same size. Enhancement of resources by nutrient addition caused a 32% increase in growth rates in experiments from a mesotrophic site, but only a 17% increase at a more eutrophic site. Additionally, copepodites at both sites showed faster development and generally larger size at stage in response to nutrient addition. Growth rates were positively related to chlorophyll concentration in the >2 μm size-fraction. A significant relationship of growth rate to body size (r ² = 0.45) emerged across a wide range of trophic status, but it was confounded with resource availability. It appears that growth in tropical copepod copepodites may be frequently limited by resources in a size-dependent manner. Received: 30 May 1997 / Accepted: 13 May 1998