Application of cryofocusing hydride generation and atomic fluorescence detection for dissolved mercury species determination in natural water samples

The concentration levels of mercury (Hg) species in natural water samples are usually low. Consequently, accurate analysis with low detection limits is still a major problem. In this work, a method was applied for the simultaneous direct determination of dissolved mercury species in water samples by on-line hydride generation (HG), cryogenic trapping (CT), gas chromatography (GC) and detection by atomic fluorescence spectrometry (AFS). The suitability of the method for real samples with different organic matter and chloride contents was evaluated by recovery experiments in synthetic and natural spiked water samples. The HG method was compared with other current available methods for mercury analysis with respect to the different fraction of mercury analysed, i.e. 'reactive', 'reducible' or total. HG derivatization and SnCl2 reduction (with and without previous oxidation with BrCl) were applied to synthetic and natural (spiked and non-spiked) water samples. The influence of chloride and dissolved organic matter concentrations was studied. The results suggest that the HG procedure is suitable for the simultaneous determination of Hg2+ and MeHg+ in surface water samples. Inorganic mercury analysed by HG (i.e. reducible) is close to the total inorganic mercury.     

Multi-objective, decision-based assessment of a water quality monitoring network in a river system

Water quality monitoring network design has historically tended to use experience, intuition and subjective judgement in locating monitoring stations. Better design procedures to optimize monitoring systems need to simultaneously identify significant planning objectives and consider a number of social, economic and environmental constraints. The consideration of multiple objectives may require further decision analysis to determine the preference weights associated with the objectives to aid in the decision-making process. This may require the application of an optimization study to extract such information from decision makers or experts and to evaluate the overall effectiveness of locating strategies. This paper assesses the optimal expansion and relocation strategies of a water quality monitoring network using a two-stage analysis. The first stage focuses on the information retrieval of preference weights with respect to the designated planning objectives. With the aid of a pre-emptive goal programming model, data analysis is applied to obtain the essential information from the questionnaire outputs. The second stage then utilizes a weighted multi-objective optimization approach to search for the optimal locating strategies of the monitoring stations in the river basin. Practical implementation is illustrated by a case study in the Kao-Ping River Basin, south Taiwan.     

Optimal and suboptimal control of anaerobic digesters

Anaerobic digester failure due to entry of inhibitors or sudden changes in the feed substrate concentration may be encompassed beneficially by applying optimal control theory. An almost proportional relationship between the dilution rate and the methane production rate leads to a simple suboptimal control law with only minor loss in performance, after the occurrence of the above mentioned events.     

Pesticide burden on some insects of economic importance in Lucknow (India)

Some insects of economic importance from Lucknow (India) have been investigated for their pesticide burden. Chlorinated pesticide residues of DDT, BHC and aldrin along with their metabolites and isomers have been detected in crop pollinating insects, honeybees (Apis indica) and butterflies (Danais chrysippus and Eurema sp.) and predators, dragonfly (Platythemis sp.) and wasps (Polistes herebreus). DDT and their metabolites were present in concentrations which varied from 231–796 ng g^–1, followed by BHC (10–60 ng g^–1), and aldrin (0.26–6.68 ng g^–1). This finding is likely to stimulate newer interest in the area of pesticide research and start meaningful investigation to find if bioaccumulated pesticides would have adverse impact on otherwise beneficial potentials of such insects in our ecosystems.     

Environmental and biological monitoring of methyl ethyl ketone (MEK)

This study was conducted to evaluate the usefulness of various biological parameters for monitoring of workers exposed to methyl ethyl ketone (MEK). Fifty male workers from a large magnetic videotape factory participated in this study. Personal air samples were collected using 3M organic vapor monitors and analysed for MEK by gas chromatography with flame ionisation detector (FID). 10 mL of urine; blood (1 mL) and exhaled air were also collected at the end of an 8-hour workshift. The headspace GC method was applied for measurement of urinary and blood MEK. MEK in expired air was analysed directly by using a GC/FID.The correlation coefficients (r) between environmental MEK and all other biological parameters measured show significant positive relationships. The r for environmental MEK and urine MEK was 0.84; for blood 0.73 and for breath 0.64. The correlation coefficients between blood and urine was 0.72; blood and breath was 0.88 and urine and breath 0.60. These findings suggest that measurements of unmetabolised MEK in blood, exhaled air and urine can be used for biological monitoring of MEK exposure. Nevertheless, laboratory methodological assessment is in favour of measuring urinary MEK as it is non-invasive and does not have to be analysed immediately after collection.     

Spectrophotometric determination of ferbam (iron(III) dimethyldithiocarbamate) in commercial sample and wheat grains using 4,7-diphenyl-1,10-phenanthroline after extraction into mesityl oxide

A procedure has been developed for the determination of iron(III) dimethyldithiocarbamate by converting it into iron(II)-bathophenanthroline complex, which is then extracted into mesityl oxide in the presence of potassium perchlorate. The absorbance is then measured at 534 nm against a reagent blank. Beer's law is obeyed over the concentration range 0.5-20 microg ml(-1) in the final solution. The method is sensitive, highly selective and can be used for the determination of ferbam in a commercial sample, and in mixtures with various dithiocarbamates (ziram, zineb, maneb, etc.) and in wheat grains.     

Mobilization of aluminium and deposition on fish gills during sea salt episodes--catchment liming as countermeasure

Episodic events may be critical with respect to aluminium (Al) toxicity in moderately acidified salmon rivers. The present work demonstrates that sea salt episodes enhance the toxicity of Al in acidic rivers. The documented sea salt episode (300 [micro sign]M Cl) mobilized positively charged Al species (0.4 to 1.1 [micro sign]M Al(i)), enhanced the Al accumulation on fish gills (0.9 to 10 [micro sign]mol g(-1) dw) and caused increased stress responses (6 to15 mM blood glucose) in fish. Accumulated Al on gills remained high several days after the episode. The presented results are based on a six-week field study in two tributary rivers on the west coast of Norway. Changes in the river water qualities and Al speciation were followed using in situ fractionation techniques. Al accumulation on gills and stress responses were followed for Atlantic salmon (Salmo salar) kept in tanks continually exposed to the changing water quality. The potential mobilization of Al from the two catchments was studied by extracting soils with diluted seawater (salinity of 3). To counteract Al toxicity, one of the tributary catchments has been limed. The potential mobility of Al by sea salt was lower in limed soils compared to acid soils, and the Al deposition on fish gills (<3.5 [micro sign]mol g(-1) dw) and associated stress responses stayed low during the sea salt episode in the river draining the limed catchment. Thus, for acid river systems in coastal areas, catchment liming should be considered as a useful countermeasure for Al toxicity.     

Organophosphate flame retardants and plasticisers in wastewater treatment plants

Previous studies have revealed that chlorinated and non-chlorinated organophosphorous flame retardants and plasticisers are important contaminants in German surface waters and it has been demonstrated that wastewater treatment plants contribute to the emission of these substances. In this study temporal development as well as elimination efficiency were determined in two wastewater treatment plants (STP) in the Ruhr/Rhine area at different stages of the wastewater treatment process. The samples were analysed for the non-chlorinated organophosphate esters tri-n-butylphosphate (TnBP), tri-iso-butylphosphate (TiBP), tris-(butoxyethyl)-phosphate (TBEP) and triphenylphosphate (TPP) and the chlorinated organophosphate esters tris-(2-chloro, 1-methylethyl)-phosphate (TCPP), tris-(2-chloro-, 1-chloromethylethyl)-phosphate (TDCP) and tris-(2-chloroethyl)-phosphate (TCEP). The study showed that there were significant differences in the elimination of chlorinated and non-chlorinated organophosphorous flame retardants. The elimination rates ranged from 57-86% for TiBP, TnBP and TBEP at both STP's. No elimination of the chlorinated flame retardants TCPP, TDCP and TCEP was observed in any of the sampled STPs. At both STPs the first treatment steps and the final filtration did not contribute to the elimination of the non-chlorinated organophosphorous flame retardants while the aeration step did. At both STPs the efficiency of the cleaning process concerning the flame retardants was comparable. Thus the type of construction of the STP was not relevant for the elimination of these substances. Additionally a strong day-to-day variation was observed, while in one STP a temporal trend for TCPP during the week was found.     

Selection and Calibration of Numerical Modeling in Flow and Water Quality

Numerical modeling is frequently used in coastal engineering research and application. One possible issue associated with using this method however, is that initial outcomes might differ from expectation. Modeling manipulation addresses this issue by changing the initial parameters which in turn affects the final output results. The advancement of modeling techniques in recent years has seen a gradual but steady accruement of knowledge regarding the relationship between input parameters and possible outputs, which has resulted in improved accuracy and efficiency methods. The advancements within this field have predominantly occurred on an individual basis and as such lack standardisation. An expert numerical modeler may use this knowledge subconsciously, yet may not know how to convey it to the model users. This paper has been written to introduce a systematic intelligent coding schema designed to organise current coastal engineering modeling manipulation knowledge into a standardised format. This system is relevant to the development of appropriate strategies for improved accuracy and efficiency as well as model modification to simulate specific real phenomena in prototype application cases.