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.     

Statistical modeling of crystalline silica exposure by trade in the construction industry using a database compiled from the literature

A quantitative determinants-of-exposure analysis of respirable crystalline silica (RCS) levels in the construction industry was performed using a database compiled from an extensive literature review. Statistical models were developed to predict work-shift exposure levels by trade. Monte Carlo simulation was used to recreate exposures derived from summarized measurements which were combined with single measurements for analysis. Modeling was performed using Tobit models within a multimodel inference framework, with year, sampling duration, type of environment, project purpose, project type, sampling strategy and use of exposure controls as potential predictors. 1346 RCS measurements were included in the analysis, of which 318 were non-detects and 228 were simulated from summary statistics. The model containing all the variables explained 22% of total variability. Apart from trade, sampling duration, year and strategy were the most influential predictors of RCS levels. The use of exposure controls was associated with an average decrease of 19% in exposure levels compared to none, and increased concentrations were found for industrial, demolition and renovation projects. Predicted geometric means for year 1999 were the highest for drilling rig operators (0.238 mg m(-3)) and tunnel construction workers (0.224 mg m(-3)), while the estimated exceedance fraction of the ACGIH TLV by trade ranged from 47% to 91%. The predicted geometric means in this study indicated important overexposure compared to the TLV. However, the low proportion of variability explained by the models suggests that the construction trade is only a moderate predictor of work-shift exposure levels. The impact of the different tasks performed during a work shift should also be assessed to provide better management and control of RCS exposure levels on construction sites.     

Validation of evacuated canisters for sampling volatile organic compounds in healthcare settings

Healthcare settings present a challenging environment for assessing low-level concentrations of specific volatile organic compounds (VOCs) in the presence of high background concentrations of alcohol from the use of hand sanitizers and surface disinfectants. The purposes of this laboratory-based project were to develop and validate a sampling and analysis methodology for quantifying low-level VOC concentrations as well as high-level alcohol concentrations found together in healthcare settings. Sampling was conducted using evacuated canisters lined with fused silica. Gas chromatography/mass spectrometry analysis was performed using preconcentration (for ppb levels) and loop injection (for ppm levels). For a select list of 14 VOCs, bias, precision, and accuracy of both the preconcentration and loop injection methods were evaluated, as was analyte stability in evacuated canisters over 30 days. Using the preconcentration (ppb-level) method, all validation criteria were met for 13 of the 14 target analytes-ethanol, acetone, methylene chloride, hexane, chloroform, benzene, methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, alpha-pinene, and limonene. Using the loop injection (ppm-level) method, all validation criteria were met for each analyte. At ppm levels, alpha-pinene and limonene remained stable over 21 days, while the rest of the analytes were stable for 30 days. All analytes remained stable over 30 days at ppb levels. This sampling and analysis approach is a viable (i.e., accurate and stable) methodology that will enable development of VOC profiles for mixed exposures experienced by healthcare workers.     

Monitoring of ozone effects on the vitality and increment of Norway spruce and European beech in the Central European forests

The ozone effect on Norway spruce (Picea abies (L) Karst.) and European beech (Fagus sylvatica L.) was studied on 48 monitoring plots in 2005-2008. These plots represent two major forest tree species stands of different ages in eight regions of the Czech Republic. The forest conditions were represented by defoliation and the annual radial increment of individual trees. The ozone exposure was assessed by using modeled values of mean annual O(3) concentration and the AOT40 index. The malondialdehyde (MDA) content of the foliage was analysed and used as an indicator of oxidative stress. The correlation analysis showed a significant relation of Norway spruce defoliation to the AOT40 exposure index, and European beech defoliation to the MDA level. The radial increment response to ozone was significant only for the European beech: (a) the correlation analysis showed its decrease with increasing AOT40; (b) the regression model showed its decrease with increasing mean annual ozone concentration only at lower altitudes (<700 m a.s.l.).     

A Multiple Criteria Decision Analysis Model Based on ELECTRE TRI-C for Erosion Risk Assessment in Agricultural Areas

This paper deals with a real-world decision-aiding problem for zoning the risk of erosion, total suspended solids emissions, and ecological consequences of their transfers towards the streams. One of these consequences is the decrease of fishes into the streams in agricultural watersheds, because of the clogging of spawning areas. Given the multiple criteria nature of the problem, the originality of our research is to adapt a new decision-aiding sorting method, ELECTRE TRI-C, for identifying risk zones in rural areas, where measures must be taken. The developed model was applied in a small watershed (Low Normandy, France) where the objective was to assess the most appropriate intervention for protecting the reproduction habitat of the salmonid fishes. Agricultural parcels were evaluated on multiple criteria for grouping them into four risk categories, which are related to risk levels as well as priorities on the improvement works. The decision-aiding sorting model is co-constructed, within a constructive approach, through an interaction process between decision-aiding analysts, environmental experts, and local actors for improving transparency and communication on the results. This model is linked with a geographical information system (GIS) for assessing a set of criteria and the visualization of the farming parcels along with their type of intervention they should be submitted to best practices. The assignment results were validated by the environmental experts. These results have a strong impact on the agricultural practices of the farmers into the watersheds. The model proposed in this paper can be considered as a useful decision aid tool in any regions for implementing public agricultural and environmental policies for protecting the ecological areas.     

Relevance of the economic crisis in chemical PM10 changes in a semi-arid industrial environment

This paper shows the changes in PM(10) levels and chemical composition in a region in southeast Spain between two periods: September 2005-August 2006 and June 2008-May 2009. PM(10) levels in this arid region, with a great number of cement, ceramic and related industries, have decreased in the second period in concordance with the reduction of industrial production due to the economic crisis and the closure of a cement plant. Annual average levels of PM(10) decreased from 41?μg?m(-3) in 2005 to 30?μg?m(-3) in 2008 (27%) and to 23?μg?m(-3) in 2009 (23%). The relative contribution of the different sources has not changed in the area in the latter period and the elements with mineral origin are the main components of the PM(10) composition. There is a reduction in the concentration of the components that have soil-related industries and crustal material resuspension as their main sources, mainly in the case of CO(3) (2-), Ca, Sr, Tl and Pb, but the seasonal patterns were the same in both periods. As a particular case, there is an uncoupling between the seasonal evolution of SO(2) and sulphates in the two study periods, which remarks the existence of a sulphate regional background that does not depend on SO(2) local emissions. The decrease of V, Ni and Tl levels reflects the reduction of the industrial activity during the crisis period, affecting mainly the ceramic sector characterised by a great decrease of Tl levels.     

Biomonitoring of polychlorinated biphenyls (PCBs) in heavily polluted aquatic environment in different fish species

The distribution and concentrations of polychlorinated biphenyls (PCBs) were determined in fish species (European perch Perca fluviatilis, northern pike Esox lucius, pike perch Sander lucioperca, wels catfish Silirus glanus, common carp Cyprinus carpio, European eel Anguilla anguilla, freshwater bream Abramis brama, goldfish Carassius auratus, and roach Rutilus rutilus) in a heavily polluted water reservoir Zemplínska ?írava (Slovakia). The study performed at two different time points 5?years apart (2004 and 2009) revealed serious PCB contamination of fish muscle tissue and significant interspecies as well as tissue-specific differences in PCB uptake by fish. Total PCBs broadly correlated with the trophic position of individual fish species within a food chain (P??0.05). The study has shown that the kind of fish, its feeding habit, and specific conditions of the habitat are mutually interrelated factors that are responsible for significant variations in fish body burdens. A tendency to PCB biomagnification was also proved in some fish species of this water reservoir.     

Groundwater contamination evolution in the Guadiamar and Agrio aquifers after the Aznalcóllar spill: assessment and environmental implications

In 1998, the Agrio and Guadiamar rivers underwent an enormous environmental disaster caused by the rupture of the Aznalcóllar tailings dam and the release of 6 hm³ of pyrite sludge and acidic water. Both rivers run over recent alluvial materials which form a small-sized aquifer which is however important because underground water feeds the flow of the rivers. This work analyzes the state of groundwater 10 years after the spill. Before the dam failure, this aquifer was already contaminated in the zone nearest to the mine, to which the impact of the spill was added. Contamination levels in the alluvial aquifer of the Agrio River have decreased remarkably. However, they are still important, with acidic pH values and high concentrations of toxic elements (maximum values of 16 mg/L of Zn and 15 mg/L of Al). There are also important levels of contamination in the Guadiamar alluvial area closest to the mine, as well as in specific zones located further south. The concentration of toxic elements is mainly controlled by pH. The evolution of contaminant levels show a sharp decrease after the first years following the spill, followed by a subsequent stabilization. It is necessary to take measures for the recovery of the aquifer because, otherwise, groundwater will continue contributing contaminants into the Agrio and Guadiamar rivers.     

Tidally driven N, P, Fe and Mn exchanges in salt marsh sediments of Tagus estuary (SW Europe)

Short-sediment cores and flooding water were collected at 0, 5, 15, 25 and 50?min of tidal inundation in the two sites colonised by pure stands of Spartina maritima (low marsh) and Sarcocornia fruticosa (high marsh) from the Rosário salt marsh (Tagus estuary, SW Europe). Concentrations of NH (4) (+) , NO (3) (-) +?NO (2) (-) and HPO (4) (2-) , Fe and Mn were measured in tidal flooding water and pore water. Flooding water is enriched in nutrients, particularly ammonium due to local discharge of untreated urban effluents. Nevertheless, NH (4) (+) and NO (3) (-) +?NO (2) (-) concentrations in flooding waters at t?=?5?min (NH (4) (+) =?246?±?7?μM, NO (3) (-) +?NO (2) (-) =?138?±?1?μM for S. fruticosa and NH (4) (+) =?256?±?8?μM, NO (3) (-) +?NO (2) (-) =?138?±?1?μM for S. maritima) rose sharply at both vegetated sites. An increase was also registered for HPO (4) (2-) and total dissolved Fe although the subsequent decrease was smoother. Advective transport induced by the two daily pulses of inundation is several orders of magnitude higher than the diffusive fluxes during submerged periods. In addition, solutes are exported from the sediment with the inundation and imported in submerged periods. The exported amount of inorganic nitrogen during tidal inundation (export of 3,200?μmol?N?m(-2)?day(-1)to the water column), is not counterbalanced by the sink of -290?μmol?N?m(-2)?day(-1) occurred during the submerged period.     

Analysis of long-term water quality for effective river health monitoring in peri-urban landscapes—a case study of the Hawkesbury–Nepean river system in NSW, Australia

The Hawkesbury–Nepean River (HNR) system in South-Eastern Australia is the main source of water supply for the Sydney Metropolitan area and is one of the more complex river systems due to the influence of urbanisation and other activities in the peri-urban landscape through which it flows. The long-term monitoring of river water quality is likely to suffer from data gaps due to funding cuts, changes in priority and related reasons. Nevertheless, we need to assess river health based on the available information. In this study, we demonstrated how the Factor Analysis (FA), Hierarchical Agglomerative Cluster Analysis (HACA) and Trend Analysis (TA) can be applied to evaluate long-term historic data sets. Six water quality parameters, viz., temperature, chlorophyll-a, dissolved oxygen, oxides of nitrogen, suspended solids and reactive silicates, measured at weekly intervals between 1985 and 2008 at 12 monitoring stations located along the 300 km length of the HNR system were evaluated to understand the human and natural influences on the river system in a peri-urban landscape. The application of FA extracted three latent factors which explained more than 70 % of the total variance of the data and related to the ‘bio-geographical’, ‘natural’ and ‘nutrient pollutant’ dimensions of the HNR system. The bio-geographical and nutrient pollution factors more likely related to the direct influence of changes and activities of peri-urban natures and accounted for approximately 50 % of variability in water quality. The application of HACA indicated two major clusters representing clean and polluted zones of the river. On the spatial scale, one cluster was represented by the upper and lower sections of the river (clean zone) and accounted for approximately 158 km of the river. The other cluster was represented by the middle section (polluted zone) with a length of approximately 98 km. Trend Analysis indicated how the point sources influence river water quality on spatio-temporal scales, taking into account the various effects of nutrient and other pollutant loads from sewerage effluents, agriculture and other point and non-point sources along the river and major tributaries of the HNR. Over the past 26 years, water temperature has significantly increased while suspended solids have significantly decreased (p?<?0.05). The analysis of water quality data through FA, HACA and TA helped to characterise the key sections and cluster the key water quality variables of the HNR system. The insights gained from this study have the potential to improve the effectiveness of river health-monitoring programs in terms of cost, time and effort, particularly in a peri-urban context.