Polychlorinated biphenyls and polybrominated diphenyl ethers in the North American atmosphere

To assess the spatial concentration variability of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the atmosphere on a large continental scale, their annually integrated air concentrations were determined in 2000/2001 using XAD-based passive air samplers (PAS). The network included 40 stations in Canada, the United States, Mexico, Belize and Costa Rica, and covered 72 degrees of latitude and longitude. Total concentrations of PCB and PBDE congeners ranged from below the detection limit to 130 ng PAS-1 and 24 ng PAS-1, respectively. PCBs displayed a large variation between urban, rural and remote sites, whereas PBDEs did not follow such a pattern. Open burning of "Penta"-containing waste may have contributed to the PBDEs detected in the air samples from rural and remote areas. Air from the Canadian Arctic had a relatively higher percentage of lighter PCB congeners than air sampled in the tropical region, which is interpreted as evidence for global fractionation.     

Alkoxy-silyl Induced Agglomeration: A New Approach for the Sustainable Removal of Microplastic from Aquatic Systems

The substance class of inert organic-chemical stressors (IOCS) describes organic-chemical (macro-) molecules, which demonstrate a high level of persistence upon entry in the ecosystem, and whose degradation is limited. These synthetically produced organic-chemical macromolecules, which are often derived from the polymerization of different monomers, are, in the form of plastics, indispensable in the everyday world. They enter the environmental compartments and cause great damage due to primary (industry, cosmetic, washing of textile), and secondary (degradation) entry. If these particles get into aquatic systems, this has fatal consequences for the ecosystem such as the death of marine animals, or bioaccumulation. Wastewater treatment plants are reaching their limits and require innovative ideas for the sustainable removal of microplastic. This article examines a new approach to the removal of polymers from aquatic systems (lab scale) by using sol–gel induced agglomeration reactions to form larger particle agglomerates. These enlarged agglomerates can be separated much more easily from the wastewater, since they float on the water surface. Separation systems, e.g. sand trap can easily be used. A further advantage is that the agglomeration can be carried out completely independently of the type, size, and amount of the trace substance concentration as well as of the external influences (pH value, temperature, pressure). Thus, this new type of particle separation can not only be used in sewage treatment plants, but can also be transferred to decentralized systems (e.g. implementation in industrial processes).

Graphical Abstract

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Role of age and injury mechanism on cervical spine injury tolerance from head contact loading

Objective: The objective of this study was to determine the influence of age and injury mechanism on cervical spine tolerance to injury from head contact loading using survival analysis.

Methods: This study analyzed data from previously conducted experiments using post mortem human subjects (PMHS). Group A tests used the upright intact head–cervical column experimental model. The inferior end of the specimen was fixed, the head was balanced by a mechanical system, and natural lordosis was removed. Specimens were placed on a testing device via a load cell. The piston applied loading at the vertex region. Spinal injuries were identified using medical images. Group B tests used the inverted head–cervical column experimental model. In one study, head–T1 specimens were fixed distally, and C7–T1 joints were oriented anteriorly, preserving lordosis. Torso mass of 16 kg was added to the specimen. In another inverted head–cervical column study, occiput–T2 columns were obtained, an artificial head was attached, T1–T2 was fixed, C4–C5 disc was maintained horizontal in the lordosis posture, and C7–T1 was unconstrained. The specimens were attached to the drop test carriage carrying a torso mass of 15 kg. A load cell at the inferior end measured neck loads in both studies. Axial neck force and age were used as the primary response variable and covariate to derive injury probability curves using survival analysis.

Results: Group A tests showed that age is a significant (P < .05) and negative covariate; that is, increasing age resulted in decreasing force for the same risk. Injuries were mainly vertebral body fractures and concentrated at one level, mid-to-lower cervical spine, and were attributed to compression-related mechanisms. However, age was not a significant covariate for the combined data from group B tests. Both group B tests produced many soft tissue injuries, at all levels, from C1 to T1. The injury mechanism was attributed to mainly extension. Multiple and noncontiguous injuries occurred. Injury probability curves, ±95% confidence intervals, and normalized confidence interval sizes representing the quality of the mean curve are given for different data sets.

Conclusions: For compression-related injuries, specimen age should be used as a covariate or individual specimen data may be prescaled to derive risk curves. For distraction- or extension-related injuries, however, specimen age need not be used as a covariate in the statistical analysis. The findings from these tests and survival analysis indicate that the age factor modulates human cervical spine tolerance to impact injury.     

When the going gets tough: Employee reactions to large-scale organizational change and the role of employee Machiavellianism

Large-scale, long-term change initiatives take time to unfold, which can be a source of uncertainty and strain. Investigating the initial 19 months of a large-scale change, we argue that during these stages, employees' change-related beliefs become more negative over time, which negatively affects their work engagement and, ultimately, increases their turnover intentions. Furthermore, we investigate the impact of a trait, Machiavellianism, on change reactions and propose that employees high in Machiavellianism react more negatively during change processes as they are especially susceptible to uncertainty and stress. We test our (cross-level) moderated mediation model in a three-wave longitudinal study among employees undergoing a large-scale change (T1: n = 1,602; T2: n = 1,113; T3: n = 759). We find that employees' beliefs about the impact and value of the change are indeed negatively related to change duration and that decreases in these perceptions come with a decline in engagement and increases in turnover intentions. Moreover, employees high in Machiavellianism react more strongly to a deterioration in change-related beliefs, showing stronger reductions in engagement and stronger increases in turnover intentions than employees low in Machiavellianism. Our study offers explanations for the negative effects of large-scale changes including an explanatory factor for disparate employee reactions to change over time.     

Applying Zonation Methods and Tabu Search to Improve the Ground‐Water Modeling1

Abstract: An optimization procedure combining zonation methods with the Tabu Search method is proposed to identify the spatial distribution of hydraulic conductivity field. Three zonation methods, Voronoi diagram (VD), multiplicatively weighted Voronoi diagram (MWVD), and pattern zonation are adopted for the parameterization purposes. With the consideration of the homogeneity and the heterogeneity, there are four spatial distributions of hydraulic conductivity designed to test whether the parameter structure can be successfully identified. The fitting residual error is first considered to determine an adequate number of zones without over parameterization. Then, the parameter uncertainty is evaluated the decision of the number of zones. The results indicate that the MWVD performs better than other two methods because the MWVD has better flexibility in describing the zonal boundaries with small number of decision variables.     

Estimated nationwide effects of pesticide spray drift on terrestrial habitats in the Netherlands

This study estimated the potential effects of pesticide drift on terrestrial ecosystems outside target areas, for the Dutch situation. A series of field trials was conducted to estimate the effects of drift on different species groups at different distances from a treated plot for different categories of pesticide: herbicides, fungicides and insecticides. Measurements of the pesticide drift deposition resulting from standard agricultural practice were used to model deposition outside the treated area. These data were then combined with national statistics on cropland and pesticide use to assess the ecological effects of pesticide drift for the Netherlands as a whole. Three scenarios were considered: the recent past (1998), the present (2005) and an optimised scenario based on 'best available practice' (2010). In the recent past the impact of herbicide drift on sensitive life stages non-target vascular plants is estimated to have exceeded the 50% effect level on 59% of adjacent linear landscape elements such as ditch banks and hedgerows. For the impact of insecticides and fungicides on non-target insects and fungi this 50% effect figure was 29% and 28% of linear elements, respectively. In the present situation, with (narrow) unsprayed buffer zones and other measures in place, these percentages are down to 41% for herbicides, 21% for insecticides and 14% for fungicides. In the optimised scenario, with a greater buffer width of 2.25m for potatoes (compared to 1.50m in 2005) and 1m for other crops (compared to 0.25 and 0.5m in 2005) and 'best available practice', these percentages can be cut to zero. In natural areas located within farming regions the 10% effect level can be reduced from 31% of such areas (1998) to 0% under conditions of 'best available practice'.     

Toxicity assessment of collected fractions from an extracted naphthenic acid mixture

Recent expansion within the oil sands industry of the Athabasca Basin of Alberta, Canada has led to increased concern regarding process-affected wastewaters produced during bitumen extraction. Naphthenic acids (NAs) have been identified as the primary toxic constituents of oil sands process-affected waters (OSPW) and studies have shown that with time, microbial degradation of lower molecular weight NAs has led to a decrease in observed toxicity. As earlier studies identified the need for an "unequivocal demonstration" of lower molecular weight NAs being the primary contributors to mixture toxicity, a study was initiated to fractionate an extracted NA mixture by molecular weight and to assess each fraction's toxicity. Successful molecular weight fractionation of a methylated NA mixture was achieved using a Kugelrohr distillation apparatus, in which fractions collected at higher boiling points contained NAs with greater total carbon content as well as greater degree of cyclicity. Assays with Vibrio fischeri bioluminescence (via Microtox assay) revealed that the lowest molecular weight NAs collected had higher potency (EC50: 41.9+/-2.8 mg l(-1)) than the highest molecular weight NAs collected (EC50: 64.9+/-7.4 mg l(-1)). Although these results support field observations of microbial degradation of low molecular weight NAs decreasing OSPW toxicity, it is not clear why larger NAs, given their greater hydrophobicity, would be less toxic.     

Neptunium(V) adsorption to calcite

The migration behavior of the actinyl ions U(VI)O₂²⁺, Np(V)O₂⁺ and Pu(V,VI)O₂^(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO₂⁺ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0–9.4) and concentration (0.4 μM–40 μM) conditions. pH is adjusted by variation of CO₂ partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85 ± 0.01 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05 ± 0.03 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased K_D values after desorption compared to adsorption.