A moving target—incorporating knowledge of the spatial ecology of fish into the assessment and management of freshwater fish populations

Freshwater fish move vertically and horizontally through the aquatic landscape for a variety of reasons, such as to find and exploit patchy resources or to locate essential habitats (e.g., for spawning). Inherent challenges exist with the assessment of fish populations because they are moving targets. We submit that quantifying and describing the spatial ecology of fish and their habitat is an important component of freshwater fishery assessment and management. With a growing number of tools available for studying the spatial ecology of fishes (e.g., telemetry, population genetics, hydroacoustics, otolith microchemistry, stable isotope analysis), new knowledge can now be generated and incorporated into biological assessment and fishery management. For example, knowing when, where, and how to deploy assessment gears is essential to inform, refine, or calibrate assessment protocols. Such information is also useful for quantifying or avoiding bycatch of imperiled species. Knowledge of habitat connectivity and usage can identify critically important migration corridors and habitats and can be used to improve our understanding of variables that influence spatial structuring of fish populations. Similarly, demographic processes are partly driven by the behavior of fish and mediated by environmental drivers. Information on these processes is critical to the development and application of realistic population dynamics models. Collectively, biological assessment, when informed by knowledge of spatial ecology, can provide managers with the ability to understand how and when fish and their habitats may be exposed to different threats. Naturally, this knowledge helps to better evaluate or develop strategies to protect the long-term viability of fishery production. Failure to understand the spatial ecology of fishes and to incorporate spatiotemporal data can bias population assessments and forecasts and potentially lead to ineffective or counterproductive management actions.     

Transport of atmospheric fine particulate matter: part 2--findings from recent field programs on the intraurban variability in fine particulate matter

Air quality field data, collected as part of the fine particulate matter Supersites Program and other field measurements programs, have been used to assess the degree of intraurban variability for various physical and chemical properties of ambient fine particulate matter. Spatial patterns vary from nearly homogeneous to quite heterogeneous, depending on the city, parameter of interest, and the approach or method used to define spatial variability. Secondary formation, which is often regional in nature, drives fine particulate matter mass and the relevant chemical components toward high intraurban spatial homogeneity. Those particulate matter components that are dominated by primary emissions within the urban area, such as black carbon and several trace elements, tend to exhibit greater spatial heterogeneity. A variety of study designs and data analysis approaches have been used to characterize intraurban variability. High temporal correlation does not imply spatial homogeneity. For example, there can be high temporal correlation but with spatial heterogeneity manifested as smooth spatial gradients, often emanating from areas of high emissions such as the urban core or industrial zones.     

Design approaches for a cycling adsorbent/photocatalyst system for indoor air purification: formaldehyde example

A kinetic model for a cycling adsorbent/photocatalyst combination for formaldehyde removal in indoor air (Chin et al. J. Catalysis 2006, 237, 29-37) was previously developed in our lab, demonstrating agreement with lab-scale batch operation data of other researchers (Shiraishi et al. Chem. Engineer. Sci. 2003, 58, 929-934). Model parameters evaluated included adsorption equilibrium and rate constants for the adsorbent (activated carbon) honeycomb rotor, and catalytic rate constant for pseudo-first-order formaldehyde destruction in the titanium dioxide photoreactor. This paper explores design consequences for this novel system. In particular, the batch parameter values are used to model both adsorbent and photocatalyst behavior for continuous operation in typical residential home challenges. Design variables, including realistic make-up air fraction, adsorbent honeycomb rotation speed, and formaldehyde source emission rate, are considered to evaluate the ability of the system to achieve World Health Organization pollutant guidelines. In all circumstances, the size of the required rotating adsorbent bed and photoreactor for single-stage operation and the resultant formaldehyde concentration in the home are calculated. The ability of how well such a system might be accommodated within the typical dimensions of commercial ventilation ducts is also considered.     

Separating the effects of organic matter-mineral interactions and organic matter chemistry on the sorption of diuron and phenanthrene

Even though it is well established that soil C content is the primary determinant of the sorption affinity of soils for non-ionic compounds, it is also clear that organic carbon-normalized sorption coefficients (K(OC)) vary considerably between soils. Two factors that may contribute to K(OC) variability are variations in organic matter chemistry between soils and interactions between organic matter and soil minerals. Here, we quantify these effects for two non-ionic sorbates-diuron and phenanthrene. The effect of organic matter-mineral interactions were evaluated by comparing K(OC) for demineralized (HF-treated) soils, with K(OC) for the corresponding whole soils. For diuron and phenanthrene, average ratios of K(OC) of the HF-treated soils to K(OC) of the whole soils were 2.5 and 2.3, respectively, indicating a substantial depression of K(OC) due to the presence of minerals in the whole soils. The effect of organic matter chemistry was determined by correlating K(OC) against distributions of C types determined using solid-state (13)C NMR spectroscopy. For diuron, K(OC) was positively correlated with aryl C and negatively correlated with O-alkyl C, for both whole and HF-treated soils, whereas for phenanthrene, these correlations were only present for the HF-treated soils. We suggest that the lack of a clear effect of organic matter chemistry on whole soil K(OC) for phenanthrene is due to an over-riding influence of organic matter-mineral interactions in this case. This hypothesis is supported by a correlation between the increase in K(OC) on HF-treatment and the soil clay content for phenanthrene, but not for diuron.     

Semipermeable membrane device (SPMD) for monitoring PCDD and PCDF levels from a paper mill effluent in the Androscoggin River, Maine, USA

Paper mill effluents may contain polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) that are normally generated due to chlorinated bleaching of pulp and paper. We used the semipermeable membrane device (SPMD) to monitor PCDD/F levels upstream and downstream of a paper mill on the Androscoggin River, in Jay (ME). Following the 36 day deployment, SPMD dialysis and cleanup, the samples were analyzed by HRGC/HRMS. Total concentrations of PCDD/Fs in SPMDs (sum of all tetra-through octachlorinated congeners) ranged from 4.71 pg g(-1) to 26.26 pg g(-1). Five out of the targeted 17 toxic congeners were detected, including: 2,3,7,8-TCDF; 1,2,3,7,8-PeCDF; 2,3,4,7,8-PeCDF; 1,2,3,4,6,7,8-HpCDD and OCDD. Permeability reference compounds (PRCs) were used for in situ calibration of the SPMD sampling rate (Rs). In all sites, water concentrations were the highest for OCDD (0.081-0.103 pg l(-1)), and the lowest for 1,2,3,7,8-PeCDF (0.005-0.009 pg l(-1)). There was not a consistent pattern of upstream-downstream gradient in the PCDD/F levels. This suggested that processes other than the mill in Jay (multiple sources, river dynamics) governed the flux of PCDD/Fs in the sampling locations. The SPMD results were validated by comparison to other studies on the Androscoggin River and elsewhere, confirming the potential of the device as a useful monitoring technique for PCDD/Fs in large river systems.     

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993–2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993–2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites.Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999–2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.     

Long-term geochemical evolution of the near field repository: insights from reactive transport modelling and experimental evidences

The KBS-3 underground nuclear waste repository concept designed by the Swedish Nuclear Fuel and Waste Management Co. (SKB) includes a bentonite buffer barrier surrounding the copper canisters and the iron insert where spent nuclear fuel will be placed. Bentonite is also part of the backfill material used to seal the access and deposition tunnels of the repository. The bentonite barrier has three main safety functions: to ensure the physical stability of the canister, to retard the intrusion of groundwater to the canisters, and in case of canister failure, to retard the migration of radionuclides to the geosphere. Laboratory experiments (< 10 years long) have provided evidence of the control exerted by accessory minerals and clay surfaces on the pore water chemistry. The evolution of the pore water chemistry will be a primordial factor on the long-term stability of the bentonite barrier, which is a key issue in the safety assessments of the KBS-3 concept.In this work we aim to study the long-term geochemical evolution of bentonite and its pore water in the evolving geochemical environment due to climate change. In order to do this, reactive transport simulations are used to predict the interaction between groundwater and bentonite which is simulated following two different pathways: (1) groundwater flow through the backfill in the deposition tunnels, eventually reaching the top of the deposition hole, and (2) direct connection between groundwater and bentonite rings through fractures in the granite crosscutting the deposition hole. The influence of changes in climate has been tested using three different waters interacting with the bentonite: present-day groundwater, water derived from ice melting, and deep-seated brine. Two commercial bentonites have been considered as buffer material, MX-80 and Deponit CA-N, and one natural clay (Friedland type) for the backfill. They show differences in the composition of the exchangeable cations and in the accessory mineral content. Results from the simulations indicate that pore water chemistry is controlled by the equilibrium with the accessory minerals, especially carbonates. pH is buffered by precipitation/dissolution of calcite and dolomite, when present. The equilibrium of these minerals is deeply influenced by gypsum dissolution and cation exchange reactions in the smectite interlayer. If carbonate minerals are initially absent in bentonite, pH is then controlled by surface acidity reactions in the hydroxyl groups at the edge sites of the clay fraction, although its buffering capacity is not as strong as the equilibrium with carbonate minerals. The redox capacity of the bentonite pore water system is mainly controlled by Fe(II)-bearing minerals (pyrite and siderite). Changes in the groundwater composition lead to variations in the cation exchange occupancy, and dissolution–precipitation of carbonate minerals and gypsum. The most significant changes in the evolution of the system are predicted when ice-melting water, which is highly diluted and alkaline, enters into the system. In this case, the dissolution of carbonate minerals is enhanced, increasing pH in the bentonite pore water. Moreover, a rapid change in the population of exchange sites in the smectite is expected due to the replacement of Na for Ca.     

Field and laboratory simulations of storm water pulses: behavioural avoidance by marine epifauna

Epifaunal communities associated with macroalgae were exposed to storm water pulses using a custom made irrigation system. Treatments included Millipore freshwater, freshwater spiked with trace metals and seawater controls to allow for the relative importance of freshwater inundation, trace metals and increased flow to be determined. Experimental pulses created conditions similar to those that occur following real storm water events. Brief storm water pulses reduced the abundance of amphipods and gastropods. Freshwater was the causative agent as there were no additional effects of trace metals on the assemblages. Laboratory assays indicated that neither direct nor latent mortality was likely following experimental pulses and that epifauna readily avoid storm water. Indirect effects upon epifauna through salinity-induced changes to algal habitats were not found in field recolonisation experiments. Results demonstrate the importance of examining the effects of pulsed contaminants under realistic exposure conditions and the need to consider ecologically relevant endpoints.     

Cyclodextrins: a new efficient absorbent to treat waste gas streams

Volatile Organic Compounds (VOCs) in the air provoke health and environmental concerns. This paper focuses on the absorption method to treat industrial polluted air loaded with VOCs. The key variable of this treatment being the choice of a suitable liquid absorbent, the aim of this research work is to investigate the effectiveness and the regeneration of a new potential family of absorbent: cyclodextrins (CDs). All CDs derivatives tested are able to decrease the Henry's law constant of toluene: a reduction of volatility up to 95% may be obtained, depending on CD nature and concentration. Moreover, absorption experiments show that beta-CD, which presents the highest absorption ability, is 250 time more efficient than water. The absorption efficiency is not totally correlated with static experiments, suggesting that, in addition to Henry's law constants and inclusion compounds stability, toluene diffusion into such solutions has to be taken into account. It is also to be noted that salt and pH variations seem to have little influence on the absorption capacity of CDs, which may be of great interest for industrial applications. Finally, since production of solid compounds was not observed during these experiments and since temperature decreases the capture ability in a drastic way, regeneration of the washing solution can be achieved by heating the solution in combination with air stripping.     

Clear effects of soil organic matter chemistry, as determined by NMR spectroscopy, on the sorption of diuron

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.