Kinetic parameter estimation for decomposition of organic peroxides by means of DSC measurements

The thermal stability of organic peroxides (cumene hydroperoxide 80 wt% and dicumyl peroxide) was studied by means of calorimetric measurement (DSC, TA Q1000) in an isotherm mode and a dynamic mode. Analysis of power profiles released in the isothermal mode was combined with the analysis of the decomposed compounds by a gas chromatograph/mass spectrometer (GC/MS) to determine the reaction mechanisms corresponding to each of the two reactions. In this work, a methodology for estimating kinetic parameters was based on the comparison of the power profile (dynamic mode) given by the model to that obtained experimentally by changing the parameters values. Parameter estimation is achieved using the mixed estimation method where a genetic algorithm is combined with a locally convergent method.     

Bioaccumulation surveillance in Milford Haven Waterway

Biomonitoring of contaminants (metals, organotins, polyaromatic hydrocarbons (PAHs), PCBs) was undertaken in Milford Haven Waterway (MHW) and a reference site in the Tywi Estuary (St Ishmael/Ferryside) during 2007–2008. Bioindicator species encompassed various uptake routes—Fucus vesiculosus (dissolved contaminants); Littorina littorea (grazer); Mytilus edulis and Cerastoderma edule (suspension feeders); and Hediste (=Nereis) diversicolor (sediments). Differences in feeding and habitat preference have subtle implications for bioaccumulation trends though, with few exceptions, contaminant burdens in MHW were higher than the Tywi reference site, reflecting inputs. Elevated metal concentrations were observed at some MHW sites, whilst As and Se (molluscs and seaweed) were consistently at the higher end of the UK range. However, for most metals, distributions in MH biota were not exceptional. Several metal-species combinations indicated increases in bioavailability upstream, which may reflect the influence of geogenic/land-based sources—perhaps enhanced by lower salinity. TBT levels in MH mussels were below OSPAR toxicity thresholds and in the Tywi were close to zero. Phenyltins were not accumulated appreciably in M. edulis, whereas some H. diversicolor populations appear subjected to localized (historical) sources. PAHs in H. diversicolor were distributed evenly across most of MHW, although acenaphthene, fluoranthene, pyrene, benzo(a)anthracene and chrysene were highest at one site near the mouth; naphthalenes in H. diversicolor were enriched in the mid-upper Haven (a pattern seen in M. edulis for most PAHs). Whilst PAH (and PCB) concentrations in MH mussels were mostly above reference and OSPAR backgrounds, they are unlikely to exceed ecotoxicological thresholds. Bivalve Condition indices (CI) were highest at the Tywi reference site and at the seaward end of MH, decreasing upstream—giving rise to several significant (negative) relationships between CI and body burdens. Despite the possible influence of salinity gradient as a complicating factor, multivariate analysis indicated that a combination of contaminants could influence the pattern in condition (and the biomarkers metallothionein and TOSC). Integrating bioaccumulation data with biological and biochemical endpoints is seen as a useful way to discriminate environmental quality of moderately contaminated areas such as MHW and to prioritise cause and effect investigations.     

Mixed response in bacterial and biochemical variables to simulated sand mining in placer-rich beach sediments,Ratnagiri, West coast of India

We investigated the influence on bacterial community and biochemical variables through mechanical disturbance of sediment-akin to small-scale mining in Kalbadevi beach, Ratnagiri, a placer-rich beach ecosystem which is a potential mining site. Changes were investigated by comparing three periods, namely phase I before disturbance, phase II just after disturbance, and phase III 24 h after disturbance as the bacterial generation time is ≤7 h. Cores from dune, berm, high-, mid-, and low-tide were examined for changes in distribution of total bacterial abundance, total direct viability (counts under aerobic and anaerobic conditions), culturability and biochemical parameters up to 40 cm depth. Results showed that bacterial abundance decreased by an order from 10⁶ cells g^− 1 sediment, while, viability reduced marginally. Culturability on different-strength nutrient broth increased by 155% during phase II. Changes in sedimentary proteins, carbohydrates, and lipids were marked at berm and dune and masked at other levels by tidal influence. Sedimentary ATP reduced drastically. During phase III, Pearson’s correlation between these variables evolved from non-significant to significant level. Thus, simulated disturbance had a mixed effect on bacterial and biochemical variables of the sediments. It had a negative impact on bacterial abundance, viability and ATP but positive impact on culturability. Viability, culturability, and ATP could act as important indicators reflecting the disturbance in the system at short time intervals. Culturability, which improved by an order, could perhaps be a fraction that contributes to restoration of the system at bacterial level. This baseline information about the potential mining site could help in developing rational approach towards sustainable harnessing of resources with minimum damage to the ecosystem.     

Monitoring water quality in reservoirs for human supply through multi-biomarker evaluation in tropical fish

Paraíba do Sul River is located at a very densely inhabited region of Brazil crossing the three most industrialized states of the country (S?o Paulo, Minas Gerais and Rio de Janeiro states). As a result, industrial and farming residues as well as urban sewage are frequently disposed without appropriate treatment. The current study aimed at investigating the water quality in three reservoirs along the Paraíba do Sul River (Ilha dos Pombos, Santa Cecília and Santa Branca), through physiological, morphological, biochemical, and genetic biomarkers. The bioindicator chosen was the catfish Pimelodus maculatus, sampled during the dry (June 2008) and rainy (February 2009) seasons. Also, some water physicochemical parameters were analyzed from the sampling sites, but displayed no alterations according to the Brazilian Agency for Water Quality Legislation. Branchial carbonic anhydrase activity was inhibited in the dry season, while renal carbonic anhydrase activity was inhibited in the rainy season in the Santa Branca reservoir, indicating disturbance of osmoregulatory and acid-base regulation processes. Histopathological alterations were observed in the gills (neoplasic and tissue hyperplasia processes) and liver (necrosis), indicating serious damage to the functional integrity of these organs. A high incidence of melanomacrophage centers was observed in the liver, suggesting an intense immune response in all reservoirs. Acetylcholinesterase and catalase activity showed also differences corroborating some morphological results. Likewise, the induction of the micronucleus and DNA damage indicate genotoxicity, but mainly in the Santa Branca reservoir. Thus, the health status of P. maculatus warrants caution in the use of the water from the 3 reservoirs for direct human consumption, particularly after the accidental spill of endosulfan in November 2008, three months before the rainy season sampling.     

Dibenzazepin hydrochloride as a new spectrophotometric reagent for determination of hydrogen peroxide in plant extracts

A rapid, simple, accurate, and sensitive visible spectrophotometric method for the determination of trace amounts of hydrogen peroxide in acidic buffer medium is reported. The proposed method is based on the oxidative coupling of Ampyrone with dibenzazepin hydrochloride by hydrogen peroxide in the buffer medium of pH?4.0 which is catalyzed by ferrous iron. The blue-colored product formed with maximum absorption at 620?nm was found to be stable for 2?h. Beer's law is obeyed for hydrogen peroxide concentration in the range of 0.03-0.42?μg?ml(-1). The optimum reaction conditions and other important optical parameters are reported. The molar absorptive and Sandell's sensitivity are found to be 5.89?×?10(4)?mol(-1)?cm(-1) and 0.57?g/cm(2), respectively. The interference due to diverse ions and complexing agents was studied. The method is successfully applied to the determination of hydrogen peroxide in green plants satisfactorily.     

Integrated approach for demarcating subsurface pollution and saline water intrusion zones in SIPCOT area: a case study from Cuddalore in Southern India

This paper deals with a systematic hydrogeological, geophysical, and hydrochemical investigations carried out in SIPCOT area in Southern India to demarcate groundwater pollution and saline intrusion through Uppanar River, which flows parallel to sea coast with high salinity (average TDS 28, 870 mg/l) due to back waters as well as discharge of industrial and domestic effluents. Hydrogeological and geophysical investigations comprising topographic survey, self-potential, multi-electrode resistivity imaging, and water quality monitoring were found the extent of saline water intrusion in the south and pockets of subsurface pollution in the north of the study area. Since the area is beset with highly permeable unconfined quaternary alluvium forming potential aquifer at shallow depth, long-term excessive pumping and influence of the River have led to lowering of the water table and degradation of water quality through increased salinity there by generating reversal of hydraulic gradient in the south. The improper management of industrial wastes and left over chemicals by closed industries has led surface and subsurface pollution in the north of the study area.     

Denitrification potential of the Northern Arabian Gulf—an experimental study

The study aims to establish denitrification potential of the Northern Arabian Gulf (NAG), as nitrogen critically affects the ocean productivity, obliterates acidity, oxidative capacity and radiative transfer capability of atmosphere. The experimental study was conducted by taking cores from intertidal zones from two different sites in North and South, referred as sites N and S; representing two distinct environmental milieu. The experiment was conducted in controlled laboratory conditions simulating the tidal cycles. Multiple cores were taken and loaded with seawater with different N concentrations, the redox potential was established for each condition. Redox potential was significantly lower at 10?cm depth compared to the surface in all cores (P?<?0.001). The redox potential at surface and at 10?cm depth was significantly lower at site S compared to site N (P?<?0.001; F?=?714.2), suggesting anaerobic sediments at site S. Effects of nitrate spiked seawater on denitrification under nonflooded and flooded conditions at the two sites were also studied. Three-way ANOVA analysis indicated that site, nitrate concentration, and flooding had significant main and interactive effects on the rate of denitrification. The results suggest that under ambient nitrate concentrations (0.03?mg NO₃-N?l^?1), 6.3?±?2.1?g NO₃-N?ha?day can be denitrified by inter-tidal zone sediments. At a nitrate concentration of 1?mg NO₃-N?l^?1, 92?±?16?g NO₃-N?ha?day may be denitrified whilst at a very high nitrate load of 10?mg NO₃-N?l^?1, the sediments may attain a rate of denitrification close to 404?±?78?g NO₃-N?ha?day.