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.     

Ecological niche segregation among five toothed whale species off the NW Iberian Peninsula using ecological tracers as multi-approach

This study aims to assess niche segregation among the five main toothed whales that frequent the NW Iberian Peninsula waters: the common dolphin, the harbour porpoise, the bottlenose dolphin, the striped dolphin and the long-finned pilot whale. We used cadmium (Cd) and stable isotope ratios (δ¹³C and δ¹⁵N) as ecological tracers to assess degree of segregation in diet/trophic level and in foraging habitat, over various time-scales. δ¹³C values highlighted different habitats, while Cd concentrations highlighted feeding differences between oceanic and neritic species. Moreover, δ¹⁵N values suggest different trophic levels of prey targeted within oceanic and neritic species. Hence, results revealed long-term ecological segregation among five toothed whales that coexist in the NWIP and demonstrated the ability of ecological tracers to discriminate ecological niches among closely related species.     

Roe and red deer as bioindicators of heavy metals contamination in north-western Poland

The present paper examines the degree of environmental contamination in areas covered by the Natura 2000 programme, located in north-western Poland, with selected heavy metals based on their concentration in target organs of roe and red deer. Lead, cadmium, copper, iron, and zinc concentrations were determined by inductively coupled plasma–atomic emission spectrometry. Residues of lead and cadmium were found in most of the analysed samples of roe and red deer organs The concentration of cadmium in the organs of the animals studied was much higher than that of lead. The median for Pb in liver and kidneys was 0.055 and 0.092 μg/g dry weight (d.w.) in roe deer, and 0.067 and 0.081 μg/g d.w. in red deer, respectively. The median for liver and kidney cadmium was 0.770 and 6.139 μg/g d.w. in roe deer, and 0.422 and 6.365 μg/g d.w. in red deer, respectively. Our study has demonstrated that this area is laden with lead and cadmium. This is evidenced by the fact that maximum permissible levels of these elements in the organs of red and roe deer, which were used as bioindicators of environmental contamination, were exceeded.     

Shifts in Microbial Communities,Microbial Biomass and Organic Matter Mineralization for Three Mediterranean Soils Contaminated By Metals

Microbial communities (phospholipid fatty acid pattern, bacterial growing strategies, eco-physiological index (EPI) and total bacteria counts, as a number of heterotrophic cuhurable bacteria), substrate-induced respiration (SIR), and nitrogen mineralization were studied in three Mediterranean soils at three different depth levels (A, B and C). Soils were experimentally treated with a final concentration of 1000 ppm of trace metals (Cu²⁺, Zn²⁺, Al³⁺, Fe²⁺, Pb²⁺, Ni²⁺, Mn²⁺, Cr³⁺ and Cd²⁺). Soils were stored in 571 plastic containers for one year, and watered with 1001 during this period. Leachate was recovered through a bottom tap. Samples of the three depths were studied. Soil microbial communities showed different effects to other studies presented in the literature, but carried out on non-Mediterranean soils. Dramatic differences were found between treated soils and untreated ones, but not between soils or horizons. the treated soil displayed a decrease in CFUs, SIR N-mineralization and EPI together with a dominance of r-growing strategists. the relative moles percent of several PLFAs, especially 15:0, 16: 1ω7, cy17: 0, br18:0 and 18: 1ω7 decreased because of the pollution of soils, whereas 10Me16, 18:2ω6, cy19:0, i16:0 and br17:0 showed higher values than in untreated soils.     

Application of Synchronous Fluorescence Spectroscopy for Characterization of the Aromatic Hydrocarbons in Sediments of the Middle Adriatic

UV-fluorescence spectroscopy method with synchronous mode of scanning was used to characterize the types of aromatic hydrocarbons in surface sediments. the sampling stations were located on two transverses between Yugoslavian and the Italian coasts in the middle of the Adriatic Sea. the preparation of sediment samples was made according to IOC/UNESCO (1982). Synchronous excitation/emission scanning were done at wavelengths from 236/260 to 516/540 nm. Since the wavelength of maximum emission is a function of fused aromatic rings in a molecule, the fluorescence spectra of each sample were divided into three intervals: 300–340, 340–400, over 400 nm, corresponding to compounds with 2, 3 and 4,5 and more rings respectively.

Large qualitative differences were established between sediment samples. PAH with 5 and more rings are more prevalent near the Italian coast.     

Spatial variogram estimation from temporally aggregated seabird count data

Seabird abundance is an important indicator for assessing impact of human activities on the marine environment. However, data collection at sea is time consuming and surveys are carried out over several consecutive days for efficiency reasons. This study investigates the validity of aggregating those data over time to estimate a spatial variogram that is representative for spatial correlation in species abundance. For this purpose we simulate four-day surveys of seabird count data that contain spatial and temporal correlation arising from temporal changes in the spatial pattern of environmental conditions. Estimates of the aggregated spatial variogram are compared to a variogram that would arise when data were collected over a single day. The study reveals that, under changing environmental conditions over surveys days, aggregating data over a four-day survey increases both the non-spatial variation in the data and the scale of spatial correlation in seabird data. Next, the effect of using an aggregated variogram on the statistical power to test the significance of an impact is investigated. The impact concerns a case of establishing an offshore wind farm resulting in seabird displacement. The study shows that both overestimation and underestimation of statistical power occurs, with power estimates differing up to a factor of two. We conclude that the spatial variation in seabird abundance can be misrepresented by using temporally aggregated data. In impact studies, such misrepresentation can lead to erroneous assessments of the ability to detect impact.     

Nonparametric circular methods for exploring environmental data

The goal of this work is to introduce nonparametric kernel methods for density and regression estimation for circular data, and illustrate their use by a brief simulation study and real data application. Apart from supplying practitioners with a license free and easy to run code for the use of these methods, our aim is also to provide solutions to practical problems that may be encountered in their application. The real data examples belong to the International Polar Year project, concerned with the environmental change in the polar regions.     

Mobilization of arsenic and other trace elements of health concern in groundwater from the Salí River Basin, Tucumán Province, Argentina

The Salí River Basin in north-west Argentina (7,000 km²) is composed of a sequence of Tertiary and Quaternary loess deposits, which have been substantially reworked by fluvial and aeolian processes. As with other areas of the Chaco-Pampean Plain, groundwater in the basin suffers a range of chemical quality problems, including arsenic (concentrations in the range of 12.2–1,660 μg L⁻¹), fluoride (50–8,740 μg L⁻¹), boron (34.0–9,550 μg L⁻¹), vanadium (30.7–300 μg L⁻¹) and uranium (0.03–125 μg L⁻¹). Shallow groundwater (depths up to 15 m) has particularly high concentrations of these elements. Exceedances above WHO (2011) guideline values are 100% for As, 35% for B, 21% for U and 17% for F. Concentrations in deep (>200 m) and artesian groundwater in the basin are also often high, though less extreme than at shallow depths. The waters are oxidizing, with often high bicarbonate concentrations (50.0–1,260 mg L⁻¹) and pH (6.28–9.24). The ultimate sources of these trace elements are the volcanic components of the loess deposits, although sorption reactions involving secondary Al and Fe oxides also regulate the distribution and mobility of trace elements in the aquifers. In addition, concentrations of chromium lie in range of 79.4–232 μg L⁻¹ in shallow groundwater, 129–250 μg L⁻¹ in deep groundwater and 110–218 μg L⁻¹ in artesian groundwater. All exceed the WHO guideline value of 50 μg L⁻¹. Their origin is likely to be predominantly geogenic, present as chromate in the ambient oxic and alkaline aquifer conditions.     

Soft song is a reliable signal of aggressive intent in song sparrows

Animals frequently use signals to modulate aggressive interactions. Establishing that a signal is aggressive or threatening requires demonstrating that it is more commonly used in agonistic contexts, that it predicts subsequent aggressive behaviors by the sender, and that receivers respond differently to this signal. Like many birds, song sparrows (Melospiza melodia) produce a low-amplitude “soft song” vocalization that has been hypothesized to be an aggressive signal. Soft song meets the first two criteria, but previous research has failed to demonstrate that soft song provokes aggression or that receivers even perceive soft song differently from normal loud song. We used a playback experiment with taxidermic mount presentation to test whether territorial male song sparrows respond differently to loud and soft song playbacks. Subjects reacted more strongly to the soft song playback by approaching the mount more closely, increasing wing wave displays, and increasing the proportion of their own songs that were soft songs, with further trends toward increasing the number of flights and attacks. These results confirm that soft song is a conventional signal of aggression in song sparrows and that increased receiver retaliation maintains its reliability.