Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters

• Selective molecularly imprinted polymer (MIP) binding gel was prepared. • MIP-DGT showed excellent uptake performance for antibiotics. • In situ measurement of antibiotics in wastewaters via MIP-DGT was developed. • The MIP-DGT method was robust, reliable, and highly sensitive. Urban wastewater is one of main sources for the introduction of antibiotics into the environment. Monitoring the concentrations of antibiotics in wastewater is necessary for estimating the amount of antibiotics discharged into the environment through urban wastewater treatment systems. In this study, we report a novel diffusive gradient in thin films (DGT) method based on molecularly imprinted polymers (MIPs) for in situ measurement of two typical antibiotics, fluoroquinolones (FQs) and sulfonamides (SAs) in urban wastewater. MIPs show specific adsorption toward their templates and their structural analogs, resulting in the selective uptake of the two target antibiotics during MIP-DGT deployment. The uptake performance of the MIP-DGTs was evaluated in the laboratory and was relatively independent of solution pH (4.0–9.0), ionic strength (1–750 mmol/L), and dissolved organic matter (DOM, 0–20 mg/L). MIP-DGT samplers were tested in the effluent of an urban wastewater treatment plant for field trials, where three SA (sulfamethoxazole, sulfapyridine, and trimethoprim) and one FQ (ofloxacin) antibiotics were detected, with concentrations ranging from 25.50 to 117.58 ng/L, which are consistent with the results measured by grab sampling. The total removal efficiency of the antibiotics was 80.1% by the treatment plant. This study demonstrates that MIP-DGT is an effective tool for in situ monitoring of trace antibiotics in complex urban wastewaters.     

Point Sampling Digital Imagery with ‘Samplepoint’

Measuring percent occurrence of objects from digital images can save time and expense relative to conventional field measurements. However, the accuracy of image analysis had, until now, not reached the level of the best conventional field measurements. Additionally, most image-analysis software programs require advanced user training to successfully analyze images. Here we present a new software program, ‘SamplePoint,’ that provides the user a single-pixel sample point and the ability to view and identify the pixel context. We found SamplePoint to allow accuracy comparable with the most accurate field-methods for ground-cover measurements. Expert use of the program requires minimal training and its ease of use allows rapid measurements from image data. We recommend SamplePoint for calibrating the threshold-detection level of image-analysis software or for making direct measurements of percent occurrence from digital images.     

Can we gain precision by sampling with probabilities proportional to size in surveying recent landscape changes in the Netherlands?

Seventy-two squares of 100 ha were selected by stratified random sampling with probabilities proportional to size (pps) to survey landscape changes in the period 1996–2003. The area of the plots times the urbanization pressure was used as a size measure. The central question of this study is whether the sampling with probabilities proportional to size leads to gain in precision compared to equal probability sampling. On average 1.03 isolated buildings per 100 ha have been built, while 0.90 buildings per 100 ha have been removed, leading to a net change of 0.13 building per 100 ha. The area with unspoiled natural relief has been reduced by 2.3 ha per 100 ha, and the length of linear relicts by 137 m per 100 ha. On average 74 m of linear green elements have been planted per 100 ha, while 106 m have been removed, leading to a net change of −31 m per 100 ha. For the state variables ‘unspoiled natural relief', ‘ linear relicts', ‘removed linear green elements', and ‘new – removed linear green elements' there is a gain in precision due to the pps-sampling. For the remaining state variables there is no gain or even a loss of precision (`new buildings', ‘removed buildings', ‘new – removed buildings', ‘new linear green elements'). Therefore, if many state variables must be monitored or when interest is not only in the change but also in the current totals, we recommend to keep things simple, and to select plots with equal probability.     

Geographic Variability in Radon Exhalation at a Rehabilitated Uranium Mine in the Northern Territory, Australia

In this study, dry season radon flux densities and radon fluxes have been determined at the rehabilitated Nabarlek uranium mine in northern Australia using conventional charcoal canisters. Environmental background levels amounted to 31± 15 milli Becquerel per m² per second (mBq m⁻² s⁻¹). Radon flux densities within the fenced rehabilitated mine area showed large variations with a maximum of 6500 mBq m⁻² s⁻¹ at an area south of the former pit characterised by a disequilibrium between ²²⁶Ra and ²³⁸U. Radon flux densities were also high above the areas of the former pit (mean 971 mBq m⁻² s⁻¹) and waste rock dump (mean 335 mBq m⁻² s⁻¹). The lower limit for the total pre-mining radon flux from the fenced area (140 ha) was estimated to 214 kBq s⁻¹, post-mining radon flux amounted to 174 kBq s⁻¹.Our study highlights that the results of radon flux studies are vitally dependant on the selection of individual survey points. We suggest the use of a randomised system for both the selection of survey points and the placement of charcoal canisters at each survey point, to avoid over estimation of radon flux densities. It is also important to emphasize the significance of having reliable pre-mining radiological data available to assess the success of rehabilitation of a uranium mine site.2006 Springer. The Australian Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Determination of Frequency for Remeasuring Ground and Vegetation Cover Factor Needed for Soil Erosion Modeling

Determining a remeasurement frequency of variables over time is required in monitoring environmental systems. This article demonstrates methods based on regression modeling and spatio-temporal variability to determine the time interval to remeasure the ground and vegetation cover factor on permanent plots for monitoring a soil erosion system. The spatio-temporal variability methods include use of historical data to predict semivariograms, modeling average temporal variability, and temporal interpolation by two-step kriging. The results show that for the cover factor, the relative errors of the prediction increase with an increased length of time interval between remeasurements when using the regression and semivariogram models. Given precision or accuracy requirements, appropriate time intervals can be determined. However, the remeasurement frequency also varies depending on the prediction interval time. As an alternative method, the range parameter of a semivariogram model can be used to quantify average temporal variability that approximates the maximum time interval between remeasurements. This method is simpler than regression and semivariogram modeling, but it requires a long-term dataset based on permanent plots. In addition, the temporal interpolation by two-step kriging is also used to determine the time interval. This method is applicable when remeasurements in time are not sufficient. If spatial and temporal remeasurements are sufficient, it can be expanded and applied to design spatial and temporal sampling simultaneously.     

Multi-stage sampling for large scale natural resources surveys: a case study of rice and waterfowl

Large-scale sample surveys to estimate abundance and distribution of organisms and their habitats are increasingly important in ecological studies. Multi-stage sampling (MSS) is especially suited to large-scale surveys because of the natural clustering of resources. To illustrate an application, we: (1) designed a stratified MSS to estimate late autumn abundance (kg/ha) of rice seeds in harvested fields as food for waterfowl wintering in the Mississippi Alluvial Valley (MAV); (2) investigated options for improving the MSS design; and (3) compared statistical and cost efficiency of MSS to simulated simple random sampling (SRS). During 2000-2002, we sampled 25-35 landowners per year, 1 or 2 fields per landowner per year, and measured seed mass in 10 soil cores collected within each field. Analysis of variance components and costs for each stage of the survey design indicated that collecting 10 soil cores per field was near the optimum of 11-15, whereas sampling >1 field per landowner provided few benefits because data from fields within landowners were highly correlated. Coefficients of variation (CV) of annual estimates of rice abundance ranged from 0.23 to 0.31 and were limited by variation among landowners and the number of landowners sampled. Design effects representing the statistical efficiency of MSS relative to SRS ranged from 3.2 to 9.0, and simulations indicated SRS would cost, on average, 1.4 times more than MSS because clustering of sample units in MSS decreased travel costs. We recommend MSS as a potential sampling strategy for large-scale natural resource surveys and specifically for future surveys of the availability of rice as food for waterfowl in the MAV and similar areas.     

Impacts of converting from leaded to unleaded gasoline on ambient lead concentrations in Jakarta metropolitan area

Total suspended particulate mater （TSP） concentrations were monitored for one year from July 2000 and for one year from April 2003 in Jakarta City. Thirteen elemental TSP components, aluminum （Al）, sodium （Na）, iron （Fe）, lead （Pb）, potassium （K）, zinc （Zn）, titanium （Ti）, manganese （Mn）, bromine （Br）, copper （Cu）, chromium （Cr）, nickel （Ni）, and vanadium （V） were analyzed by a sequential X-ray fluorescence spectrometer. Al, Na, Fe, K, and Pb were major components at most of the sampling locations in 2000. However, only Pb in 2003 dramatically decreased to one tenth. The phase-out of leaded gasoline began on July 1, 2001 in Jakarta City and lead content in gasoline decreased to one tenth, too. The decrease in Pb concentration was a result of the phase-out of leaded gasoline, as lead emissions mainly are exhaust gas from vehicles.     

Which compounds contribute most to elevated airborne exposure and corresponding health risks in the Western Balkans?

A majority of ongoing monitoring of persistent organic pollutants (POPs) is currently focused on chemicals emphasized in the Stockholm Convention. Quantitative detection of other substances (especially those with numerous anthropogenic sources such as polyaromatic hydrocarbons (PAHs)) is, however, also needed since their concentrations are usually several orders of magnitude higher. A goal of this study was to determine how various groups of compounds contribute to total human health risks at the variety of sampling sites in the region of Western Balkan. Distribution of the risks between the gas and particulate phases was also addressed. Results showed that inhalation exposure to organochlorine pesticides (OCPs) does not represent a significant risk to humans, while polychlorinated biphenyls (PCBs) re-volatilized to the atmosphere from contaminated soils and buildings can pose a problem. PCB evaporation from primary sources (currently used PCB-filled transformers or non-adequate storage facilities) generally resulted in much higher atmospheric concentrations than evaporation from the secondary sources (soils at the sites of war destructions). A majority of the human health risks at the urban sites were associated with PAHs. Between 83 and 94% of the cumulative risk at such sites was assigned to chemicals sorbed to particles, and out of it, PAHs were responsible for 99%.     

A soil sampling intercomparison exercise for the ALMERA network

Soil sampling and analysis for radionuclides after an accidental or routine release is a key factor for the dose calculation to members of the public, and for the establishment of possible countermeasures. The IAEA organized for selected laboratories of the ALMERA (Analytical Laboratories for the Measurement of Environmental Radioactivity) network a Soil Sampling Intercomparison Exercise (IAEA/SIE/01) with the objective of comparing soil sampling procedures used by different laboratories. The ALMERA network is a world-wide network of analytical laboratories located in IAEA member states capable of providing reliable and timely analysis of environmental samples in the event of an accidental or intentional release of radioactivity. Ten ALMERA laboratories were selected to participate in the sampling exercise. The soil sampling intercomparison exercise took place in November 2005 in an agricultural area qualified as a “reference site”, aimed at assessing the uncertainties associated with soil sampling in agricultural, semi-natural, urban and contaminated environments and suitable for performing sampling intercomparison. In this paper, the laboratories sampling performance were evaluated.     

Benzene Exposure Assessment at Indoor, Outdoor and Personal Levels. The French Contribution to the Life MACBETH Programme

Many VOC represent hazards to human health through chronic exposure. Recent European and world-wide legislation proposes limit values for ambient concentrations of these compounds. However, very little experimental data exists for true population exposure. In 1996, the European MACBETH initiative set out to measure population exposure to benzene in six European cities. This study details the French contribution to this program. Six campaigns were carried out, each comprising measurements at 100 outdoor sites and the participation of 50 non-smoking volunteers who wore personal samplers and had passive monitors installed in their homes. Iso-concentration maps were drawn for each campaign and the results showed that outdoor concentrations were significantly lower than indoors. Almost 75% of the volunteers were exposed to mean concentrations higher than the limit value of 5µgm³. It is demonstrated that personal exposure levels cannot be deduced simply by combining indoor and outdoor background concentrations. It is also shown that there is need for better knowledge of the contributions to overall exposure of outdoor microenvironments and the authors hope that future European directives will take this into account.