Some issues relating to the use of perfluorooctanesulfonate (PFOS) samples as reference standards

Samples of potassium perfluorooctanesulfonate (PFOSK) from three suppliers were analyzed by LC-ESI-MS/MS for purity and by LC-ESI-MS for the percentage of linear isomer present. Our data indicated that the purity ranged from 80% to 98% and the percentages of linear isomer from 67% to 79%. The proportion of branched isomers present in the samples was also estimated using (19)F NMR. These results agreed quite closely with those found by LC-ESI-MS indicating that there is essentially no difference in overall SIM response factor for the branched isomers vs. that of the linear isomer. Several further observations relevant to the use of standards when analyzing for PFOS were encountered during this study. It appears unlikely that matrix effects attributable to the cation (sodium or potassium) present in PFOSNa or PFOSK internal standards is an issue. In seeking potential matrix effects, it was found that the chromatography was improved substantially when the standard was injected as a solution in 80:20 methanol/water rather than 100% methanol. Notably, in concert with the improvement in chromatography, an increase of about 10% in response was observed. In some closely related studies, when (18)O(2) mass-labeled perfluorohexanesulfonate was used as an internal standard, the actual and theoretical concentration ratios matched closely those for related native sulfonates as long as they did not co-elute. However, when they did co-elute, the peak intensities of the native species were enhanced by about 5%, while those of the labeled compound were suppressed by a similar amount. If this effect were not taken into account, the concentration of the native would be inflated by 10%.     

Contaminant-induced irreversible changes in properties of the soil-vadose-aquifer zone: an overview

Most studies on contaminant interactions with the subsurface environment focus on contaminant transport, retention and persistence, and on potential remediation of polluted soils, vadose zones and aquifers. Changes in the soil-vadose-aquifer zone (SVAZ) matrix and properties, caused by human activities, are thus usually considered to be deviations from a normal geochemical environment, which will disappear by natural processes or by specific remediation procedures. However, contaminants may also cause, under specific conditions, irreversible changes in SVAZ properties. In this critical overview, we discuss a different aspect of contaminant-SVAZ interactions: irreversible changes in natural SVAZ properties as a result of anthropogenically-induced chemical contamination. We survey selected research results that illustrate various aspects of such phenomena, in soils, aquifers and the vadose zone. Grouping contaminants according to major and trace elements, we observe that major elements can irreversibly affect water transmission and other physical and chemical properties of the SVAZ, mainly in the liquid phase, while trace elements affect mostly the solid phase matrix.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Making a life in the physical sciences

As a practicing physical chemist, I argue that the challenges faced by the physical sciences have more parallels with organization science than it might first appear. While the physical sciences do represent a strong paradigm endeavor, many of the same issues that were raised in the article “Making a life in the field of organizational science” arise in physical sciences. An essential difference between the physical sciences and organization science is the essentially capital intensive nature of our research. Ironically, the constant pursuit of the requisite research dollars leads to substantial similarity between the fields. The state of academic physical sciences is analyzed in this context informed by the current state of research funding in the United States. Copyright © 2008 John Wiley & Sons, Ltd.     

Relating Background NO2 Concentrations in Air to Air Mass History Using Non-Parametric Regression Methods: Application at Two Background Sites in Ireland

The concentration of nitrogen dioxide (NO₂) in background air varies temporally and spatially and is influenced by meteorological and anthropogenic factors. Background concentrations used in local air quality modelling studies have a significant effect on the accuracy of the overall result and when based on short-term monitoring data, variation in concentrations with air mass history is often unaccounted for. The current paper presents a powerful tool for the quantification and separation of local and regional air mass effects on background air quality. The origin of and the regions traversed by an air mass prior to reaching a receptor has been modelled using HYsplit-4. Trajectories (between 12 and 96?h duration) were defined based on the frequency with which they passed into 16 predefined compass quadrants and each represented as a vector. Using this vector as the predictor variable and the background concentration as the response variable, non-parametric regression using a Gaussian kernel function was carried out. A graphical output indicated the trajectory direction of maximum NO₂ concentration, while allowing distinction to be made between spurious and true peaks. In all cases, air mass history was found to have a statistically significant effect on NO₂ concentrations. Incorporating emissions data into the analysis local and regional effects were separated and quantified. It was found that emissions in the UK and Europe have a significant effect on background NO₂ concentrations in Ireland and in some instances supersede domestic emissions. The methods can be used to identify source regions, separate local and regional effects and improve predictions of background concentrations based on limited monitoring data. In particular, the results highlight the importance of considering air mass history when assessing background concentration levels for use in local air quality modelling studies.     

Impacts of groundwater metal loads from bedrock fractures on water quality of a mountain stream

Acid mine drainage and metal loads from hardrock mines to surface waters is a significant problem in the western USA and many parts of the world. Mines often occur in mountain environments with fractured bedrock aquifers that serve as pathways for metals transport to streams. This study evaluates impacts from current and potential future groundwater metal (Cd, Cu, and Zn) loads from fractures underlying the Gilt Edge Mine, South Dakota, on concentrations in Strawberry Creek using existing flow and water quality data and simple mixing/dilution mass balance models. Results showed that metal loads from bedrock fractures to the creek currently contribute <1% of total loads. Even if background water quality is achieved upstream in Strawberry Creek, fracture metal loads would be <5%. Fracture loads could increase substantially and cause stream water quality standards exceedances once groundwater with elevated metals concentrations in the aquifer matrix migrates to the fractures and discharges to the stream. Potential future metal loads from an upstream fracture would contribute a small proportion of the total load relative to current loads in the stream. Cd has the highest stream concentrations relative to standards. Even if all stream water was treated to remove 90% of the Cd, the standard would still not be achieved. At a fracture farther downstream, the Cd standard can only be met if the upstream water is treated achieving a 90% reduction in Cd concentrations and the median stream flow is maintained.     

The problem of estimating recent genetic connectivity in a changing world

Accurate understanding of population connectivity is important to conservation because dispersal can play an important role in population dynamics, microevolution, and assessments of extirpation risk and population rescue. Genetic methods are increasingly used to infer population connectivity because advances in technology have made them more advantageous (e.g., cost effective) relative to ecological methods. Given the reductions in wildlife population connectivity since the Industrial Revolution and more recent drastic reductions from habitat loss, it is important to know the accuracy of and biases in genetic connectivity estimators when connectivity has declined recently. Using simulated data, we investigated the accuracy and bias of 2 common estimators of migration (movement of individuals among populations) rate. We focused on the timing of the connectivity change and the magnitude of that change on the estimates of migration by using a coalescent‐based method (Migrate‐n) and a disequilibrium‐based method (BayesAss). Contrary to expectations, when historically high connectivity had declined recently: (i) both methods over‐estimated recent migration rates; (ii) the coalescent‐based method (Migrate‐n) provided better estimates of recent migration rate than the disequilibrium‐based method (BayesAss); (iii) the coalescent‐based method did not accurately reflect long‐term genetic connectivity. Overall, our results highlight the problems with comparing coalescent and disequilibrium estimates to make inferences about the effects of recent landscape change on genetic connectivity among populations. We found that contrasting these 2 estimates to make inferences about genetic‐connectivity changes over time could lead to inaccurate conclusions.