Seasonal Variation of Toxic Benzene Emissions in Petroleum Refinery

Petroleum refineries are largest chemical industries that are responsible for the emission of several pollutants into the atmosphere. Benzene is among the most important air pollutants that are emitted by petroleum refineries, since they are involved in almost every refinery process. Volatile organic compounds (VOCs) are a major group of air pollutants, which play a critical role in atmospheric chemistry. These contribute to toxic oxidants, which are harmful to ecosystem, human health and atmosphere. The variability of pollutants is an important factor in determining human exposure to these chemicals. The ambient air concentrations of benzene were measured in several sites around the Digboi petroleum refinery, near the city of Gowahati in northeast India, during winter and summer 2004. The seasonal and spatial variations of the ambient air concentrations of this benzene were investigated and analyzed. An estimation of the contribution of the refinery to the measured atmospheric levels of benzene was also performed. The ambient air mixing ratios of benzene in a large area outside the refinery was generally low, in ppbv range, much lower than the ambient air quality standards. This article presents the temporal and spatial variation of air pollution in and around petroleum refinery and showed that no health risk due to benzene is present in the areas adjacent to the refinery.     

Investigation of heavy metal contaminations in the lower Sakarya river water and sediments

In this work, water and sediment samples were collected from three different stations located along the Sakarya river between May and September 2003. Lead, copper, chromium, zinc, nickel and cadmium concentrations were determined by using solvent extraction and flame atomic absorption spectrometric method. The results show that differences based upon sampling times, regions, sediment and water samples were observed. The mean levels of copper, nickel, chromium, lead, cadmium, zinc for sediment samples are; 4.630 μg g⁻¹, 13.520 μg g⁻¹, 8.780 μg g⁻¹, 2.550 μg g⁻¹, 9.990 μg g⁻¹ and for water samples are; 0.851 μg g⁻¹, 1.050 μg g⁻¹, 0.027 μg g⁻¹, 1.786 μg g⁻¹, 0.236 μg g⁻¹, 0.173 μg g⁻¹, respectively.     

Water quality assessment of Ogun river, South West Nigeria

The quality of Ogun river in South-West, Nigeria was studied by a field survey for a period of 1 year (covering dry season and rainy season). Water samples were collected from thirteen sites and analysed for physico-chemical and bacteriological parameters as well as heavy metals using standard methods. Generally, the values obtained for turbidity, phosphate, oil and grease, iron and faecal coliform from all the sites in both seasons were above the maximum acceptable limit set by the World Health Organization (WHO) for drinking water. Also, the manganese content from all the sites in the dry season, lead concentrations from three sites in the dry season and cadmium concentrations from some sites in both seasons were above the WHO limit. The values obtained for total dissolved solids, dissolved oxygen and chloride at site M in the dry season and nitrate at site J in the rainy season were also above the WHO limit. Pollution of Ogun river water along its course is evidenced by the high concentrations of pollution indicators, nutrients and trace metals above the acceptable limit. This poses a health risk to several rural communities who rely on the river primarily as their source of domestic water. The study showed a need for continuous pollution monitoring programme of surface waters in Nigeria.     

Growth performance and biochemical responses of three rice (Oryza sativa L.) cultivars grown in fly-ash amended soil

The disposal of fly-ash (FA) from coal-fired power stations causes significant economic and environmental problems. Use of such contaminated sites for crop production and use of contaminated water for irrigation not only decreases crop productivity but also poses health hazards to humans due to accumulation of toxic metals in edible grains. In the present investigation, three rice cultivars viz., Saryu-52, Sabha-5204, and Pant-4 were grown in garden soil (GS, control) and various amendments (10%, 25%, 50%, 75% and 100%) of FA for a period of 90 days and effect on growth and productivity of plant was evaluated vis-a-vis metal accumulation in the plants. The toxicity of FA at higher concentration (50%) was reflected by the reduction in photosynthetic pigments, protein and growth parameters viz., plant height, root biomass, number of tillers, grain and straw weight. However, at lower concentrations (10-25%), FA enhanced growth of the plants as evident by the increase of studied growth parameters. The cysteine and non-protein thiol (NP-SH) content showed increase in their levels up to 100% FA as compared to control, however, maximum content was found at 25% FA in Saryu-52 and Pant-4 and at 50% FA in Sabha-5204. Accumulation of Fe, Si, Cu, Zn, Mn, Ni, Cd and As was investigated in roots, leaves and seeds of the plants. Fe accumulation was maximum in all the parts of plant followed by Si and both showed more translocation to leaves while Mn, Zn, Cu, Ni and Cd showed lower accumulation and most of the metal was confined to roots in all the three cultivars. As was accumulated only in leaves and was not found to be in detectable levels in roots and seeds. The metal accumulation order in three rice cultivars was Fe > Si > Mn > Zn > Ni > Cu > Cd > As in all the plant parts. The results showed that rice varieties Saryu-52 and Sabha-5204 were more tolerant and could show improved growth and yield in lower FA application doses as compared to Pant-4. Thus, Sabha-5204 and Saryu-52 are found suitable for cultivation in FA amended agricultural soils for better crop yields.     

HPLC-MSn and GC-MS methods to study sunlight and UV-lamp degradations of 1-amino-5-naphthalene sulfonate

HPLC-DAD, HPLC-MS/MS, GC-MS and spectrophotometric methods are employed to investigate the degradation process of sodium 1-amino-5-naphthalene sulfonate (1A5NS) aqueous solutions, when exposed to sunlight and UV-lamp (254 nm) irradiations. Experimental results show that both sunlight and 254 nm UV-lamp irradiations destroy the chemical and give rise to major degradation products, characterised by the same m/z ratios. Degradation times are lower for sunlight irradiation, for which a t(1/2) value of 137.4 min has been evaluated, in comparison with the value of t(1/2) of 26.8 min, observed for UV-lamp irradiation. The degradation pathway and the structures of the degradation products are proposed.     

Dioxin screening in fish product by pattern recognition of biomarkers

Two alternative, cost- and time-effective dioxin screening methods relying on two categories of potential lipid biomarkers were investigated. A dioxin range varying from 1.1 to 47.1 pg PCDD/F TEQ-WHO/g lipid using 64 fish meal samples was used for model calibration. The methods were based on multivariate models using either (1) fatty acid composition monitored by GC-FID or (2) fluorescence landscape signals analysed using the PARAFAC model and in both cases predicting dioxin content as pgPCDD/F TEQ-WHO/g lipid. In both cases, Partial Least Squares (PLS) regression was performed for predicting the dioxin content of a sample. The GC-FID data analyses was based on automatic peak alignment and integration, enabling extraction of the area of 140 peaks from the gas chromatograms, as opposed to the 31 fatty acids usually considered for fish oil characterisation. In addition to classic PLS employing the whole dataset for calibration, a two-step local PLS modeling approach was performed based upon an initial selection of k number of calibration samples providing the best match to the prediction sample using a so-called k Nearest Neighbors (kNN) approach, then followed by PLS calibration on these kNN selected samples for dioxin prediction. Fluorescence spectroscopy offers a promising non-invasive and ultra-rapid technique, with less than two minutes analysis time. However, fluorescence spectroscopy using the pattern recognition "kNN-PLS" yielded a correlation of 0.76 (r2) and a high root mean square error of prediction of 11.4 pg PCDD/F TEQ-WHO/g lipid. The predictions were improved when the PLS calibration was performed on all the sample with a root mean square error of prediction of 7.0 pg PCDD/F TEQ-WHO/g lipid. Unfortunately, these results failed to demonstrate the potential of fluorophore monitoring as a screening method. In contrast, the overall best screening performance was obtained with the fatty acid profile, when the kNN-PLS combination employed for pattern recognition (kNN) all the areas of the 140 detected peaks and the PLS regression used the areas of 46 selected peaks. This "kNN-PLS" prediction with three latent variables and based upon the 12 nearest neighbors selected out of the 64 x 2 fatty acid profiles (duplicate analyses), yielded a correlation of 0.85 (r2) and a root mean square error of prediction of 2.1 pg PCDD/F TEQ-WHO/g lipid and resulted in a total analysis time of one and half hour per sample.     

Cellular alterations in different organs of European sea bass Dicentrarchus labrax (L.) exposed to cadmium

Specimens of farmed European sea bass (Dicentrarchus labrax L., 1758) were exposed to different cadmium (Cd) concentrations (4.47, 5.63, 7.08 and 8.91 mg l(-1)) for 24 and 48 h. The effects of Cd on numbers of some cell types and structures (i.e., chloride cells, CCs; macrophage aggregates, MAs; rodlet cells, RCs) and on structure and ultrastructure of the main organs (gill, liver, intestine, kidney) were studied with routine process for light and transmission electron microscopy. Following cadmium exposure, the numbers of branchial CCs as well as intestinal and renal RCs increased significantly within 24h. Increase in metal concentration did not affect the magnitude of the numerical increment of the aforementioned cells. Moreover, in treated fish (24 and 48 h) the numbers of MAs in both head kidney and spleen were significantly higher than in control conspecifics, whilst the global area of MAs was less influenced by the acute treatment. In exposed sea bass, all the examined organs exhibited cellular modifications which appeared time- and dose-dependent. The gills showed telangectasia, lamellar fusion, oedema, epithelial lifting and leukocyte infiltration. In the liver, kidney and intestine acute cell swelling and vacuolization were common. Ultrastructurally the alterations observed frequently in hepatocytes, tubular epithelial cells and enterocytes included presence of numerous myelinoid bodies, damaged mitochondria, dilatation of endoplasmic reticulum, high number of lysosomes and autophagolysosomes. In intestinal and kidney tubular epithelia of treated fish, rodlet cells displayed some anomalies like dilatation of nuclear envelope, cytoplasmic vacuolization, presence of myelinoid bodies, rodlets degeneration and extensive discharge activity.     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Lichen and moss bags as monitoring devices in urban areas. Part II: trace element content in living and dead biomonitors and comparison with synthetic materials

Lobes of the lichen Pseudevernia furfuracea (L.) Zopf and shoots of the moss Hypnum cupressiforme Hedw. were subjected to different treatments (water washing, oven drying, HNO3 washing, NH4-oxalate extraction) to assess the influence of vitality on accumulation efficiency, during a 6-week exposure in bags in two Italian cities, Trieste and Naples. No trend emerged between treatments, in terms of accumulation ability, for major and trace elements. Only water-washed lichens showed an increased C and N content after exposure in both cities. Element concentrations generally reached higher values in mosses than in lichens, especially for Al, Fe, and Zn (both cities), and for Cu, Mg and Na (Naples). Surface development strongly influenced accumulation capacity of the biomonitors. Quartzose and cation exchange filters revealed, on a weight basis, a poor performance. In urban environments, surface interception of atmospheric particulate seems to play a major role in accumulation, irrespective of organism vitality.     

Plant senescence: a mechanism for nutrient release in temperate agricultural wetlands

The beneficial uptake of nutrients by wetland plants is countered to some extent by nutrient release back into the aquatic environment due to vegetative die-back. This current study examined whether Leersia oryzoides, a common wetland plant, exhibits luxury uptake of nutrients from simulated farm runoff. The study also tested whether with subsequent decomposition, these nutrients are released back into the water column. When exposed to elevated (>2mg/L N and P) runoff, L. oryzoides assimilated significantly higher concentrations of nitrogen (p<0.001) and phosphorus (p<0.001) in above-ground biomass as compared to non-enriched treatments (<0.05 mg/L N and P). Subsequently, senescence of enriched above-ground biomass yielded significantly higher concentrations of phosphorus (2.19+/-0.84 mg P/L). Using L. oryzoides as our model, this study demonstrates nitrogen and phosphorus sequestration during the growing season and release of phosphorus in the winter.