Comprehensive two-dimensional gas chromatography time of flight mass spectrometry (GC×GC-TOFMS) for environmental forensic investigations in developing countries

The disposal and dumping of toxic waste is a matter of growing concern in developing countries, including South Africa. Frequently these countries do not possess access to gas chromatography-high resolution mass spectrometry (GC-HRMS) for the determination of persistent organic pollutants (POPs). This publication describes an alternative approach to the investigation of toxic waste using comprehensive gas chromatography coupled to time of flight mass spectrometry (GC × GC-TOFMS). The technology permits both comprehensive screening of toxic samples for numerous classes of organic pollutants and also quantitative analysis for the individual compounds. This paper describes the use of this technique by analysing samples obtained from a hazardous waste treatment facility in South Africa. After sampling and extraction the samples were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and four dioxin-like non-ortho substituted polychlorinated biphenyls (PCBs). The quantitative values, as well as detection limits, obtained using the GC × GC-TOFMS methodology compares well with those obtained using GC-HRMS; the accepted benchmark technology for this analysis. Although GC × GC-TOFMS is not a target compound analytical technique (as is GC-HRMS), it is possible to obtain information on numerous other classes of organic pollutants present in the samples in one analytical run. This is not possible with GC-HRMS. Several different column combinations have been investigated for handling very complex waste samples and suggestions are presented for the most suitable combination.     

Release of silver nanoparticles from outdoor facades

In this study we investigate the release of metallic silver nanoparticles (Ag-NP) from paints used for outdoor applications. A facade panel mounted on a model house was exposed to ambient weather conditions over a period of one year. The runoff volume of individual rain events was determined and the silver and titanium concentrations of 36 out of 65 runoff events were measured. Selected samples were prepared for electron microscopic analysis. A strong leaching of the Ag-NP was observed during the initial runoff events with a maximum concentration of 145 μ Ag/l. After a period of one year, more than 30% of the Ag-NP were released to the environment. Particles were mostly <15 nm and are released as composite colloids attached to the organic binders of the paint. Microscopic results indicate that the Ag-NP are likely transformed to considerably less toxic forms such as Ag₂S.     

Using prognostic model-generated meteorological output in the AERMOD dispersion model: an illustrative application in Philadelphia, PA

In this study, we introduce the prospect of using prognostic model-generated meteorological output as input to steady-state dispersion models by identifying possible advantages and disadvantages and by presenting a comparative analysis. Because output from prognostic meteorological models is now routinely available and is used for Eulerian and Lagrangian air quality modeling applications, we explore the possibility of using such data in lieu of traditional National Weather Service (NWS) data for dispersion models. We apply these data in an urban application where comparisons can be made between the two meteorological input data types. Using the U.S. Environment Protection Agency's American Meteorological Society/U.S. Environmental Protection Agency Regulatory Model (AERMOD) air quality dispersion model, hourly and annual average concentrations of benzene are estimated for the Philadelphia, PA, area using both hourly MM5 model-generated meteorological output and meteorological data taken from the NWS site at the Philadelphia International Airport. Our intent is to stimulate a discussion of the relevant issues and inspire future work that examines many of the questions raised in this paper.     

Human dietary intake of organochlorines from Baltic herring: implications of individual fish variability and fisheries management

This study examines the extent to which Finnish human dietary intake of organochlorines (PCDD/Fs and PCBs) originating from Northern Baltic herring can be influenced by fisheries management. This was investigated by estimation of human intake using versatile modeling tools (e.g., a herring population model and a bioenergetics model). We used a probabilistic approach to account for the variation in human intake of organochlorines originating from the variation among herring individuals. Our estimates were compared with present precautionary limits and recommendation for use. The results show that present consumption levels and frequencies of herring give a high probability of exceeding recommended intake limits of PCDD/Fs and PCBs. Furthermore, our results clearly demonstrate that in the risk management of dioxinlike organochlorines, regulating fishing (in this case increasing fishing pressure) is a far less effective way to decrease the risk than regulating the consumption of herring. Increased fishing would only slightly decrease organochlorine concentrations of herring in the Finnish fish market.     

Mercury contamination in three species of anuran amphibians from the Cache Creek Watershed, California, USA

Fish and wildlife may bioaccumulate mercury (Hg) to levels that adversely affect reproduction, growth, and survival. Sources of Hg within the Cache Creek Watershed in northern California have been identified, and concentrations of Hg in invertebrates and fish have been documented. However, bioaccumulation of Hg by amphibians has not been evaluated. In this study, adult and juvenile American bullfrogs (Lithobates catesbeianus) and foothill yellow-legged frogs (Rana boylii), adult Northern Pacific treefrogs (Pseudacris regilla), and larval bullfrogs were collected and analyzed for total Hg. One or more species of amphibians from 40% of the 35 sites had mean Hg concentrations greater than the US Environmental Protection Agency’s tissue residue criterion for fish (0.3 μg/g). Of the bullfrog tissues analyzed, the liver had the highest concentrations of both total Hg and methyl mercury. Total Hg in carcasses of bullfrogs was highly correlated with total Hg in leg muscle, the tissue most often consumed by humans.     

Verification of a depth-integrated sample arm as a means to reduce solids stratification bias in urban stormwater sampling

A new water sample collection system was developed to improve representation of solids entrained in urban stormwater by integrating water-quality samples from the entire water column, rather than a single, fixed point. The depth-integrated sample arm (DISA) was better able to characterize suspended-sediment concentration and particle size distribution compared to fixed-point methods when tested in a controlled laboratory environment. Median suspended-sediment concentrations overestimated the actual concentration by 49 and 7% when sampling the water column at 3- and 4-points spaced vertically throughout the water column, respectively. Comparatively, sampling only at the bottom of the pipe, the fixed-point overestimated the actual concentration by 96%. The fixed-point sampler also showed a coarser particle size distribution compared to the DISA which was better able to reproduce the average distribution of particles in the water column over a range of hydraulic conditions. These results emphasize the need for a water sample collection system that integrates the entire water column, rather than a single, fixed point to properly characterize the concentration and distribution of particles entrained in stormwater pipe flow.     

Statistical treatment for the wet bias in tree-ring chronologies: a case study from the Interior West,USA

Dendroclimatic research has long assumed a linear relationship between tree-ring increment and climate variables. However, ring width frequently underestimates extremely wet years, a phenomenon we refer to as ‘wet bias’. In this paper, we present statistical evidence for wet bias that is obscured by the assumption of linearity. To improve tree-ring-climate modeling, we take into account wet bias by introducing two modified linear regression models: a linear spline regression (LSR) and a likelihood-based wet bias adjusted linear regression (WBALR), in comparison with a quadratic regression (QR) model. Using gridded precipitation data and tree-ring indices of multiple species from various sites in Utah, both LSR and WBALR show a significant improvement over the linear regression model and out-perform QR in terms of in-sample \({R}^{2}\) and out-of-sample MSE. This further shows that the wet bias emerges from nonlinearity of tree-ring chronologies in reconstructing precipitation. The pattern and extent of wet bias varies by species, by site, and by precipitation regime, making it difficult to generalize the mechanisms behind its cause. However, it is likely that dis-coupling between precipitation amounts (e.g., percent received as rain/snow or percent infiltrating the soil) and its availability to trees (e.g., root zone dynamics), is the primary mechanism driving wet bias.     

Agricultural vulnerability over the Chinese Loess Plateau in response to climate change: Exposure,sensitivity, and adaptive capacity

Understanding how the vulnerability of agricultural production to climate change can differ spatially has practical significance to sustainable management of agricultural systems worldwide. Accordingly, this study developed a conceptual framework to assess the agricultural vulnerability of 243 rural counties on the Chinese Loess Plateau. Indicators representing the climate/agriculture interface were selected to describe exposure and sensitivity, while stocks of certain capitals were used to describe adaptive capacity. A vulnerability index for each county was calculated and the spatial distribution was mapped. Results showed that exposure, sensitivity, and adaptive capacity occur independently, with most contributing indicator values concentrated in a narrow range after normalization. Within the 49 most vulnerable counties, which together encompass 81 % of the vulnerability index range, 42 were characterized by high exposure and sensitivity but low adaptive capacity. The most vulnerable area was found to be located in the central northeast–southwest belt of Loess Plateau. Adaptation measures for both ecological restoration and economic development are needed and potential adaptation options need further investigation.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0727-8) contains supplementary material, which is available to authorized users.