Modelling the environmental degradation of water contaminants. Kinetics and mechanism of the riboflavin-sensitised-photooxidation of phenolic compounds

The aerobic visible-light-photosensitised irradiation of methanolic solutions of either of the phenolic-type contaminants model compounds (ArOH) p-phenylphenol (PP), p-nitrophenol (NP) and phenol (Ph), and for two additional phenolic derivatives, namely p-chlorophenol (ClP) and p-methoxyphenol (MeOP), used in some experiments, was carried out. Employing the natural pigment riboflavin (Rf) as a sensitiser, the degradation of both the ArOH and the very sensitiser was observed. A complex mechanism, common for all the ArOH studied, operates. It involves superoxide radical anion (O₂^√−) and singlet molecular oxygen (O₂(¹Δ_g)) reactions. Maintaining Rf in sensitising concentrations levels (≈0.02 mM), the mechanism is highly dependent on the concentration of the ArOH. Kinetic experiments of oxygen and substrate consumption, static fluorescence, laser flash photolysis and time-resolved phosophorescence detection of O₂(¹Δ_g) demonstrate that at ArOH concentrations in the order of 10 mM, no chemical transformation occurs due to the complete quenching of Rf singlet excited state. When ArOH is present in concentrations in the order of mM or lower, O₂^√− is generated from the corresponding Rf radical anion, which is produced by electron transfer reaction from the ArOH to triplet excited Rf. The determined reaction rate constants for this step show a fairly good correlation with the electron-donor capabilities for Ph, PP, NP, ClP and MeOP. In this context, the main oxidative species is O₂^√−, since O₂(¹Δ_g) is quenched in an exclusive physical fashion by the ArOH. The production of O₂^√− regenerates Rf impeding the total degradation of the sensitiser. This kinetic scheme could partially model the fate of ArOH in aquatic media containing natural photosensitisers, under environmental conditions.     

On-road vehicle particulate matter and gaseous emission distributions in Las Vegas, Nevada, compared with other areas

During the spring and summer of 2000, 2001, and 2002, gaseous and particulate matter (PM) fuel-based emission factors for approximately 150,000 low-tailpipe, individual vehicles in the Las Vegas, NV, area were measured via on-road remote sensing. For the gaseous pollutants (carbon monoxide, hydrocarbons, and nitrogen oxide), a commercial vehicle emissions remote sensing system (VERSS) was used. The PM emissions were determined using a Lidar-based VERSS. Emission distributions and their shapes were analyzed and compared with previous studies. The large skewness of the distributions is evident for both gaseous pollutants and PM and has important implications for emission reduction policies, because the majority of emissions are attributed to a small fraction of vehicles. Results of this Las Vegas study and studies at other geographical locations were compared. The gaseous pollutants were found to be close to those measured by VERSS in other U.S. cities. The PM emission factors for spark ignition and diesel vehicles are in the range of previous tunnel and dynamometer studies.     

Ankle fracture patterns in drivers are associated with femoral fracture,higher BMI,and advanced age

Objective: Despite advances in vehicle safety systems, motor vehicle crashes continue to cause ankle fractures. This study attempts to provide insight into the mechanisms of injury and to identify the at-risk population groups.

Methods: A study was made of ankle fractures patients treated at an urban level 1 trauma center following motor vehicle crashes, with a concurrent analysis of a nationally representative crash data set. The national data set focused on ankle fractures in drivers involved in frontal crashes. Statistical analysis was applied to the national data set to identify factors associated with fracture risk.

Results: Malleolar fractures occurred most frequently in the driver's right foot due to pedal interaction. The majority of complex/open fractures occurred in the left foot due to interaction with the vehicle floor. These fractures occurred in association with a femoral fracture, but their broad injury pattern suggests a range of fracture causation mechanisms. The statistical analysis indicated that the risk of fracture increased with increasing driver body mass index (BMI) and age.

Conclusions: Efforts to reduce the risk of driver ankle injury should focus on right foot and pedal interaction. The range of injury patterns identified here suggest that efforts to minimize driver ankle fracture risk will likely need to consider injury tolerances for flexion, pronation/supination, and axial loading in order to capture the full range of injury mechanisms. In the clinical environment, physicians examining drivers after a frontal crash should consider those who are older or obese or who have severe femoral injury without concurrent head injury as highly suspicious for an ankle injury.     

Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

Contrasting diel patterns in vertical movement and locomotor activity of whale sharks at Ningaloo Reef

Activity patterns of animals often relate to environmental variables such as food availability and predation pressure. Technological advances are providing us with new tools to monitor and better understand these activity patterns. We used animal-attached data loggers recording acceleration and depth to compare activity patterns and vertical habitat use of whale sharks (Rhincodon typus) at Ningaloo Reef, Western Australia. Whale sharks showed a moderate reverse diel vertical migration but exhibited a clear crepuscular pattern in locomotory activity. Peak activity occurred at sunset, whereas vertical movement peaked prior to this. Typical ram surface filter feeding could be identified and occurred primarily during sunset and the first hours of night. At such times, direct observations indicated whale sharks were feeding on tropical krill swarms. Kinematic analysis of postural data and data from vertical movement suggests that whale sharks at Ningaloo spend ~8 min per day actively ram surface filter feeding. Considering the high biomass present in krill schools, it is estimated that whale sharks at Ningaloo have a similar energy intake as those at other aggregation sites. Diel patterns in activity and diving behaviour suggest that whale sharks have tuned their diving behaviour in anticipation of the formation of these high-density patches which appear to only be periodically, but predictably available at sunset. Our results confirm that diel patterns in vertical habitat selection and vertical movements do not necessarily reflect patterns in activity and foraging behaviour. Direct quantification of activity and behaviour is required in gaining accurate representation of diel activity patterns.     

Shifting prey selection generates contrasting herbivore dynamics within a large-mammal predator-prey web

Shifting prey selection has been identified as a mechanism potentially regulating predator-prey interactions, but it may also lead to different outcomes, especially in more complex systems with multiple prey species available. We assessed changing prey selection by lions, the major predator for 12 large herbivore species in South Africa's Kruger National Park. The database was provided by records of found carcasses ascribed to kills by lions assembled over 70 years, coupled with counts of changing prey abundance extending over 30 years. Wildebeest and zebra constituted the most favored prey species during the early portion of the study period, while selection for buffalo rose in the south of the park after a severe drought increased their vulnerability. Rainfall had a negative influence on the proportional representation of buffalo in lion kills, but wildebeest and zebra appeared less susceptible to being killed under conditions of low rainfall. Selection by lions for alternative prey species, including giraffe, kudu, waterbuck, and warthog, was influenced by the changing relative abundance and vulnerability of the three principal prey species. Simultaneous declines in the abundance of rarer antelope species were associated with a sharp increase in selection for these species at a time when all three principal prey species were less available. Hence shifting prey selection by lions affected the dynamics of herbivore populations in different ways: promoting contrasting responses by principal prey species to rainfall variation, while apparently being the main cause of sharp declines by alternative prey species under certain conditions. Accordingly, adaptive responses by predators, to both the changing relative abundance of the principal prey species, and other conditions affecting the relative vulnerability of various species, should be taken into account to understand the interactive dynamics of multispecies predator-prey webs.     

Nutrient pathways and their susceptibility to past and future change in the Eurasian Arctic Ocean

Climate change is altering nutrient cycling within the Arctic Ocean, having knock-on effects to Arctic ecosystems. Primary production in the Arctic is principally nitrogen-limited, particularly in the western Pacific-dominated regions where denitrification exacerbates nitrogen loss. The nutrient status of the eastern Eurasian Arctic remains under debate. In the Barents Sea, primary production has increased by 88% since 1998. To support this rapid increase in productivity, either the standing stock of nutrients has been depleted, or the external nutrient supply has increased. Atlantic water inflow, enhanced mixing, benthic nitrogen cycling, and land–ocean interaction have the potential to alter the nutrient supply through addition, dilution or removal. Here we use new datasets from the Changing Arctic Ocean program alongside historical datasets to assess how nitrate and phosphate concentrations may be changing in response to these processes. We highlight how nutrient dynamics may continue to change, why this is important for regional and international policy-making and suggest relevant research priorities for the future.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-021-01673-0.