Cattle egrets as a biosentinels of persistent organic pollutants exposure

We investigated selected chlorinated pollutants (β-HCH, γ-HCH, DDDs, DDEs, o,p′-DDT, p,p′-DDT, heptachlor, aldrin, dieldrin, and endrin) in the Lahore and the Sialkot districts of Pakistan, using eggs of cattle egret (Bubulcus ibis) collected during May and June 2007. The pollutant with highest level and frequency was ΣDDT, followed by β-HCH, γ-HCH, heptachlor, aldrin, dieldrin, and endrin in descending order. The concentration(s) were significantly higher in Sialkot heronry for all the pollutants (except p,p′-DDT) than in Lahore. The values for DDTs, β-HCH, γ-HCH, and heptachlor were significantly higher (p < 0.05) in the egg(s) than in sediment(s) and in the chicks’ diet, due to biomagnification. Among DDTs analogues, p,p′-DDD was the major contaminant with >60 % of total DDT burden, reflecting the widespread aged as well as recent use of DDT as well as anaerobic degradation (DDD/DDE > 1 in many cases) in the nearby paddy soils. In few samples, p,p′-DDT/(DDD + DDE) > 0.5 suggested the recent emission patterns from surrounding contaminated areas of demolished DDT units and obsolete pesticide stores. The higher levels of HCHs (i.e., β-HCH) in the samples collected from Sialkot indicate exposure from long-term agricultural use. Overall, concentrations of all studied POPs were less than the threshold levels known to affect reproduction. Nevertheless, total DDTs and/or HCHs burdens in some eggs contained concentrations of greater than what would educe adverse effects on birds. This is among few studies on OCPs exposure to avian species, which provide the evidence of Pakistan’s contribution toward the Global POPs emission.     

Adult respiratory distress syndrome in human organophosphate poisoning cases

Adult respiratory distress syndrome (ARDS) is a clinical syndrome which occurs due to various direct or indirect noxious agents and pyhsical mechanisms. One of the etiological factors is ingested chemicals (e.g. paraquat, ethylene glycol). The organophosphorous (OP) insecticides are the most toxic and frequently encountered chemicals that produce poisoning in humans. Studies were undertaken to investigate whether OP insecticides may produce ARDS. Fifteen autopsy cases due to suicidal OP insecticide poisoning were investigated. Toxicological analyses were performed with a gas chromatography-nitrogen phosphorous detector (GC-NPD). Methamidophos, dimefox and dichlorvos were the detected OP. Lungs were examined macroscopically. Two cases showed features compatible with ARDS in which the only cause of death was OP poisoning. Due to the severity of ARDS it is important to assess insecticidal exposure in an attempt to enhance survival patterns following OP poisoning in patients in order to initiate therapy.     

Application of electrochemical reactor divided by cellulosic membrane for optimized simultaneous removal of phenols,chromium, and ammonia from tannery effluents

The post treatment of simulated tannery wastewater was evaluated in an electrochemical oxidation process under galvanostatic conditions. A continuous flow reactor divided by a cellulosic membrane consisted of Ti/SnO₂–Sb anodes and iron cathodes was used. Central composite design and response surface methodology (RSM) were applied to investigate the effects of six operational parameters, namely initial concentration of total phenols (TPh), total chromium (TCr), total ammonia nitrogen (TAN), flow rate (Q), current intensity (I), and electrode surface area (A). Effectiveness of the innovative cellulosic membrane was proven by considerable pH variations in the anolyte and catholyte chambers. A faster removal rate was observed for TPh and TAN, followed by TCr. The treatment level was very sensitive to Q and I in the studied ranges. RSM showed the removal efficiencies of 78.14%, 63.42%, and 86.09% for TPh, TCr, and TAN, respectively, are achieved under optimal conditions with consumption of only 9.03 kWh m^?3 electrical energy. Chlorinated compounds such as chloroform, 2,4-dichlorophenol, and chlorobenzene were detected as the degradation intermediates. According to the obtained results, electrolysis in the divided cell with cellulosic membrane is a practical, cost-effective method for advanced treatment of tannery effluents.     

Determination of cobalt by air-assisted liquid–liquid microextraction

Abstract

A rapid and selective technique for extraction, preconcentration and determination of trace amounts of cobalt in water and pharmaceutical samples by air-assisted liquid–liquid microextraction combined with flame atomic absorption spectrometry is proposed. 1-Nitroso-2-naphthol is used as a complexing agent and 1-octanol as an extraction solvent. Parameters relevant for analytical effectivity, i.e. pH of sample solution, concentration of complexing agent, volume of extraction solvent, and number of extraction cycles are optimized using a Box–Behnken design. At optimum conditions, a dynamic linear range of 5–600?µg L^?1 is obtained, with a limit of detection of 1.2?µg L^?1. The method is used for determination of Co(II) in environmental water and pharmaceutical samples.     

Oxidative stress in the freshwater cyprinid crucian carp (Carassius carassius L.) upon chronic exposure to endosulfan

Oxidative stress and antioxidant responses of crucian carp, upon chronic exposure to endosulfan, were evaluated in vivo. The lethal concentration (LC_50–96?h) was 70 μg L^?1; on its basis, the fish were exposed to endosulfan at 20, 35, and 50 μg L^?1 and autopsy was done on days 1, 2, 3, 4, 7, 14, 21, 28, and 35. Lipid peroxidation was induced in a concentration-dependent manner, being highest at 50 μg L^?1 (3/4 LC_{50–96 h}, sub-lethal concentration-I, SL-I) on day 4 (720% versus control), followed in its extent (490%) at 30 μg L^?1 (1/2 LC_{50–96 h}, sub-lethal concentration-II, SL-II) on day 7 and lowest (260%) at 10 μg L^?1 (1/4 LC_{50–96 h}, sub-lethal concentration-III, SL-III) on day 14. Glutathione showed a concentration- and time-dependent elevation in the initial phase, with highest level on day 4 (180%) at SL-I, but showed significant reduction in all test concentrations from day 21 of post-exposure. Superoxide dismutase was decreased significantly throughout the study, with highest reduction (63%) on day 4 at SL-I; catalase increased in all test concentrations up to day 14 but showed a significant decrease from the day 28 of post-exposure. The potential role of these parameters as indicators of pesticide pollution in aquatic systems is discussed.     

Humic substances. Part II†: Photophysical,photochemical and free radical characteristics

The effects of mercury (HgCl₂) on cell population, chlorophyll a concentration and rates of photosynthesis and excretion were investigated in the phytoplanktonic species Dunaliella minuta in laboratory cultures. Mercury, above 25ppb inhibited both cell population and chlorophyll a concentration approximately to the same extent, whereas the photosynthetic rate was inhibited to a significantly lesser degree. Although, the total photosynthetic rate of the tested organism was reduced, above a threshold concentration, the photosynthetic activity was not reduced under these conditions, but it was in fact significantly greater than that in the control culture. This may suggest that in D. minuta the inhibitory effect of mercury is primarily on cell division rather than cellular photosynthesis, which is enhanced by the fact mercury caused a significant increase of the mean cell volume. Mercury, also, decreased the growth rate and final cell yield. The excretory rate was markedly increased at concentrations ≥ 250 ppb of mercury, but at lower concentrations it tended to depend more on the physiological state of cells than on mercury concentration. In the different cultures, the photosynthetic activity showed variations which occurred without major changes in the chlorophyll a content per cell, which remained almost constant and independent of variations in cell size and growth conditions.     

Mechanistic aspects of the thermal formation of halogenated organic compounds including polychlorinated dibenzo‐p‐dioxins. Part V†: Hypotheses and summary

The hypotheses on the de novo syntheses of polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo‐p‐dioxins (PCDDs), based on known literature, are presented. Polychlorinated benzenes and polychlorinated phenols are probably key intermediates.

In the present article, hypotheses that may account for the presence of polychlorinated dibenzofurans (PCDFs) and dibenzo‐p‐dioxins (PCDDs) in the effluents from municipal and industrial incinerators are put forward. These hypotheses are based on the previously surveyed literature (Ref. 203–206) and experimental results on laboratory scale and thermodynamic calculations are considered. The interconnections of various reaction steps are speculative and no technological information was added to account for conditions in real incinerators. Conclusion of the discussions on the related subject matter, presented in the Parts I‐IV (Ref. 203–206), are also described in this paper.     

Photochemistry of halogenated benzene derivatives. part xii.∗ effects of sodium nitrite on the environmental phototransformation of bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) herbicide in water: The photoincorporation of nitrite ions into bromoxynil

Photoreactions of the herbicide bromoxynil (3,5‐dibromo‐4‐hydroxybenzonitrile) (1) were extensively studied in water containing various concentrations of sodium nitrite with radiation of wavelengths around 313 nm. In the absence of NaNO₂, the quantum yields for the photodecomposition of the herbicide I amounted to 0.054±0.005, while such data was in the range of 0.047 ±0.005 to 0.023 ±0.003 in the presence of 0.5 to 25.0 × 10^‐3 m of the inorganic salt. These quantum yield data for the phototransformation of 1 without and with the presence of sodium nitrite followed the Stern‐Volmer equation. The rates of the photolytic destruction of bromoxynil (1) in water were slower in the presence than in the absence of NaNO₂. For example, the irradiation of the 7.8 x 10^‐6M aqueous solution of 1 in the presence of 10 mM sodium nitrite gave rise to the production of three main photoproducts, viz., 3‐bromo‐4‐hydroxy‐5‐nitrobenzonitrile (2), 4‐hydroxy‐3‐nitrobenzonitrile (3), and an “unidentified photoproduct”; 4. In the case of this photoreaction of compound 1, the percentages of maximum concentration of the photoproducts 2, 3, and 4 were achieved after 14, 44.5, and 60‐min photolyses of 1, respectively; the starting material 1 completely disappeared after 60‐min photolysis. The photoproducts 2 and 3 were identified through the interpretation of the GC‐MS data. Both thhe mass and FT‐IR spectra of the product 4 indicated the possible presence of a COOH group in 4.     

Heavy metals distribution and risk assessment in soils affected by tannery effluents

Effluents collected from tanneries in Sialkot showed considerably higher levels of heavy metals. Sodium (12 660.91 mg/L) among macronutrients and Cr (592.20 mg/L) among heavy metals were found in the highest concentrations. Effluent parameters, i.e. biological oxygen demand (BOD; 12.40), chemical oxygen demand (COD; 16.53), Cd (5.90), Cr (592.20) and Fe (18.59) were the respective times higher than Pakistan National Environmental Quality Standards and their continuous unchecked discharge into agricultural soils poses a potential risk. Mean concentrations (mg/L) of Cr (592.20), Ni (2.66), Mn (1.16), Fe (37.17), Zn (0.90), Cd (0.59) and Pb (1.18) in this study exceeded levels recorded to date from different tanning hubs in Pakistan. Factor analysis/principal components analysis (FA/PCA) for the effluent parameters resulted in six varimax factors, i.e. VF1 (salinity, electrical conductivity, total dissolved solids, chloride, phosphate, BOD and COD; including characteristic tannery effluent features), VF2 (pH, Cr and alkalinity; tanning operations), VF3 (Cd and Pb; dyeing processes), VF4 (Mn and Fe; finishing operations), VF5 (Ni; retaining processes) and VF6 (hardness, Ca and Cu; bating processes). Cluster analysis performed on metal data resulted in three clusters confirming metal–metal relations obtained either from FA/PCA or a correlation matrix. The results of this study are useful for heavy metal source apportionment, assessment of risk to peripheral soils and the future management of environments around tanneries.     

Sol-gel immobilisation of methyl parathion degrading bacteria isolated from agricultural areas of Pakistan

The following areas are discussed in this paper: immobilisation of bacterial consortium in sol-gel; methyl parathion degradation and bioremediation applications; evaluation of indigenous bacterial isolates of contaminated soils. Bacterial strains were isolated from agricultural areas of Pakistan which were contaminated with methyl parathion. A bacterial consortium of seven (out of 64) Enterobacteriaceae isolates including Citrobacter, Enterobacter and Proteus vulgaris capable of degrading methyl parathion (enzyme activity ranging 410–675 mU mL^?1 for individual isolates and 982 mU/mL for consortium) was selected and subsequently immobilised in tetraethyl orthosilicate (TEOS) and sodium-silicate-based sol-gel matrices. Cell viability of suspended and immobilised bacterial consortium was monitored using a minimal salt medium supplemented with methyl parathion. The results indicate that sol-gel immobilisation can be helpful to increase the shelf life of methyl parathion degrading bacterial strains along with preservation of biological activity for bioremediation applications in field.