The effects of dissolved organic matter and pH on sampling rates for polar organic chemical integrative samplers (POCIS)

The effect of solution pH and levels of dissolved organic matter (DOM) on the sampling rates for model pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substance (EDS) by polar organic chemical integrative samplers (POCIS) was investigated in laboratory experiments. A commercially available POCIS configuration containing neutral Oasis HLB (hydrophilic-lipophilic balance) resin (i.e. pharmaceutical POCIS) and two POCIS configurations prepared in-house containing MAX and MCX anion and cation exchange resins, respectively were tested for uptake of 21 model PPCPs and EDS, including acidic, phenolic, basic and neutral compounds. Laboratory experiments were conducted with dechlorinated tap water over a pH range of 3, 7 and 9. The effects of DOM were studied using natural water from an oligotrophic lake in Ontario, Canada (i.e. Plastic Lake) spiked with different amounts of DOM (the concentration of dissolved organic carbon ranged from 3 to 5 mg L⁻¹ in uptake experiments). In experiments with the commercial (HLB) POCIS, the MCX-POCIS and the MAX-POCIS, the sampling rates generally increased with pH for basic compounds and declined with pH for acidic compounds. However, the sampling rates were relatively constant across the pH range for phenols with high pKa values (i.e. bisphenol A, estrone, estradiol, triclosan) and for the neutral pharmaceutical, carbamazepine. Thus, uptake was greatest when the amount of the neutral species in solution was maximized relative to the ionized species. Although the solution pH affected the uptake of some model ionic compounds, the effect was by less than a factor of 3. There was no significant effect of DOM on sampling rates from Plastic Lake. However, uptake rates in different aqueous matrixes declined in the order of deionized water > Plastic Lake water > dechlorinated tap water, so other parameters must affect uptake into POCIS, although this influence will be minor. MAX-POCIS and MCX-POCIS showed little advantage over the commercial POCIS configuration for monitoring in natural waters.     

Flexible foraging movements of leatherback turtles across the North Atlantic Ocean

Some marine species have been shown to target foraging at particular hotspots of high prey abundance. However, we show here that in the year after a nesting season, female leatherback turtles (Dermochelys coriacea) in the Atlantic generally spend relatively little time in fixed hotspots, especially those with a surface signature revealed in satellite imagery, but rather tend to have a pattern of near continuous traveling. Associated with this traveling, distinct changes in dive behavior indicate that turtles constantly fine tune their foraging behavior and diel activity patterns in association with local conditions. Switches between nocturnal vs. diurnal activity are rare in the animal kingdom but may be essential for survival on a diet of gelatinous zooplankton where patches of high prey availability are rare. These results indicate that in their first year after nesting, leatherback turtles do not fit the general model of migration where responses to resources are suppressed during transit. However, their behavior may be different in their sabbatical years away from nesting beaches. Our results highlight the importance of whole-ocean fishing gear regulations to minimize turtle bycatch.     

Kinetics of low frequency sonodegradation of linear alkylbenzene sulfonate solutions

The decomposition of sodium dodecylbenzene sulfonate (SDBS) in water by means of ultrasound irradiation at 20kHz was investigated. Experiments were conducted at surfactant concentrations of 175, 260 and 350 mg l(-1), liquid volumes of 120, 170 and 220 ml, temperatures of 20, 30 and 45 degrees C and applied power of 40, 80 and 125 W. The extent of degradation was followed monitoring substrate and organic carbon concentrations, while hydrogen peroxide concentration was also measured; the latter is a product of water sonolysis due to hydroxyl radical recombination. 80% SDBS conversion was achieved after 120 min of sonication at 125 W and 30 degrees C; nonetheless, SDBS and its degradation intermediates proved difficult to oxidise as only about 20-25% of the initial carbon content was transformed to carbon dioxide. At the initial stages of the reaction, degradation rate appears to be only weakly dependent on the substrate concentration with the rate increasing from 3.1 to 4 mg l(-1)min(-1) with increasing concentration from 175 to 350 mg l(-1). Degradation appears to occur at the bubble-liquid interface through hydroxyl radical-mediated reactions whose role was established by performing experiments in the presence of radical scavengers, namely potassium bromide and sodium benzoate. Degradation rates increased with increasing power and decreasing temperature and volume.     

Toxaphene in minke whales (Balaenoptera acutorostrata) from the North Atlantic

Toxaphene contamination of minke whales (Balaenoptera acutorostrata) from North Atlantic waters was examined for the first time. Total toxaphene and SigmaCHB (sum of 11 chlorobornanes) concentrations in blubber samples ranged from 170+/-110 and 41+/-39 ng/g lipid weight (l.w.) for female minke whales from southeastern Greenland to 5800+/-4100 and 1100+/-780 ng/g l.w. for males from the North Sea, respectively. Very large variations in toxaphene concentrations among sampling areas were observed suggesting a spatial segregation of minke whales. However, much of the apparent geographical discrimination was explained by the seasonal fluctuation of animal fat mass. Patterns of CHBs in males revealed that recalcitrant CHBs were in higher proportions in animals from the more easterly areas than in animals from the more westerly areas. This trend may be influenced by the predominance of the US, over the European, input of toxaphene to North Atlantic waters.     

Investigation of the generation of hydroxyl radicals and their oxidative role in the presence of heterogeneous copper catalysts

The presence and impact of hydroxyl radicals generated via the catalytic decomposition of H(2)O(2) over heterogeneous copper catalysts were investigated by using two detection methods, an electron spin resonance-spin trapping method and a chemical probe method. Detection of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct signal and formation of 4-chlorocatechol during the oxidation of a 4-chlorophenol substrate demonstrated that the three heterogeneous copper catalysts employed here (CuO, Cu/Al(2)O(3) and CuO.ZnO/Al(2)O(3)) were capable of generating hydroxyl radicals in combination with H(2)O(2). The oxidative mechanism of the hydroxyl radical in the presence of heterogeneous copper catalysts is discussed with regard to the further oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH adduct and hydroxylated products of 4-chlorophenol oxidation. Interestingly, integration of the 5,5-dimethyl-1-pyrroline-N-oxide-OH adduct signal could not be used to reliably measure the total amount of hydroxyl radicals generated as a result of oxidative attack on the adduct. This may be as a result of locally higher hydroxyl radical concentrations in the presence of a heterogeneous catalyst leading to further unwanted oxidation of the (5,5-dimethyl-1-pyrroline-N-oxide)-OH.     

Group size and relative competitive ability: geometric progressions as a conceptual tool

Contrary to the assumptions of many previous theoretical models, group size has recently been shown in experiments to have an effect on the relative (as well as absolute) competitive abilities of group members. Here we introduce a novel and effective mathematical tool for describing how relative competitive ability will change for any two specified individuals within a group as group size changes. We show that there is no simple general rule for describing how relative competitive ability will change with group size. A subsequent empirical test of the model helps to illustrate that very specific knowledge of the system under study is needed in order to produce robust predictions. Received: 23 December 1998 / Received in revised form: 26 July 1999 / Accepted: 2 October 1999     

The pattern of early growth trajectories affects adult breeding performance

Early environmental conditions can influence the pattern of growth and development. While poor conditions generally cause slower growth, normal adult size can still be reached if growth accelerates or is prolonged once conditions improve, but such catch-up growth may have deleterious effects later in life. Here we investigate for the first time how decelerating as well as accelerating growth trajectories, manipulated independently of food supply, affect subsequent breeding performance. In order to alter growth rates we subjected juvenile three-spined sticklebacks Gasterosteus aculeatus to a short period of altered environmental temperature (high, intermediate, or low), after which all fish had the same (intermediate) temperature regime. In addition, the perceived time stress (until the onset of the spawning season) was manipulated by conducting the experiment twice (in the winter and in the spring immediately prior to breeding) and by exposing half of the fish in each experiment to a delayed photoperiod (two months behind ambient). We found that fish showed full growth compensation, such that in all treatments they were of the same average size by the start of the breeding season. However, those compensating for low temperatures earlier in life (i.e., who then showed an accelerated growth trajectory) had reduced reproductive investment over the following two breeding seasons (males, reduced sexual ornaments and speed of building nests; females, reduced first clutch size, mean egg size, and eggs produced per year). Moreover, these deleterious effects were strongest when the perceived time available for growth compensation prior to breeding was shortest. In contrast, those fish with a decelerating growth trajectory as a result of exposure to high temperatures early in life showed an improved breeding performance compared to steadily growing controls. These results clearly demonstrate that both the shape of the growth trajectory (independent of food supply) and the time available for growth compensation have broad-reaching and prolonged effects on breeding performance, with ecological conditions that prompt catch-up growth just prior to the breeding season being especially damaging for both sexes.     

Threats of illegal,unregulated, and unreported fishing to biodiversity and food security in the Republic of the Congo

Illegal, unregulated, and unreported (IUU) fishing poses a major threat to effective management of marine resources, affecting biodiversity and communities dependent on these coastal resources. Spatiotemporal patterns of industrial fisheries in developing countries are often poorly understood, and global efforts to describe spatial patterns of fishing vessel activity are currently based on automatic identification system (AIS) data. However, AIS is often not a legal requirement on fishing vessels, likely resulting in underestimates of the scale and distribution of legal and illegal fishing activity, which could have significant ramifications for targeted enforcement efforts and the management of fisheries resources. To help address this knowledge gap, we analyzed 3 years of vessel monitoring system (VMS) data in partnership with the national fisheries department in the Republic of the Congo to describe the behavior of national and distant-water industrial fleets operating in these waters. We found that the spatial footprint of the industrial fisheries fleet encompassed over one-quarter of the Exclusive Economic Zone. On average, 73% of fishing activity took place on the continental shelf (waters shallower than 200 m). Our findings highlight that VMS is not acting as a deterrent or being effectively used as a proactive management tool. As much as 33% (13% on average) of fishing effort occurred in prohibited areas set aside to protect biodiversity, including artisanal fisheries resources, and the distant-water fleet responsible for as much as 84% of this illegal activity. Given the growth in industrial and distant-water fleets across the region, as well as low levels of management and enforcement, these findings highlight that there is an urgent need for the global community to help strengthen regional and national capacity to analyze national scale data sets if efforts to combat IUU fishing are to be effective.     

Impact of Socio-demographic Factors on Willingness to Pay for the Reduction of a Future Health Risk

Knowledge of socio-demographic factors affecting attitudes to and perception of risk is an important instrument in enhancing efficiencies of interventions. The authors evaluated whether socio-demographic variables affected attitudes to an environmental issue (securing future drinking water). An important aspect was the delay between time of environmental pollution and time of human exposure and thereby potential health risk. Gender, education, place of residence and age all influenced the extent to which individuals were willing to allocate present resources to alleviate a future problem. Specifically, people above the age of 50 appeared more reluctant to pay for an intervention against a future potential health threat. The authors found a significant correlation between attitude and willingness to pay (WTP). In the authors' scenarios, the WTP variable worked more as a dichotomous variable than as a continuous variable, stressing the importance and relevance of the WTP=0 answers.