Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.     

Using Wet-FGD systems for mercury removal

A plan to control mercury emissions to the atmosphere and to establish mercury emission limits has recently been elaborated by the European Commission, making it necessary to devise an efficient and cost effective mercury removal technology. Towards this end wet flue gas desulfurization units appear as a promising option for multi-pollutant control. However, more investigation on mercury removal and a greater mercury removal efficiency are required to achieve this objective. In the present work scrubber chemistry and the application of various solid additives to enhance mercury removal in wet scrubbers is evaluated. The results obtained show a significant correlation between mercury removal efficiency and the pH of the scrubber slurry and SO2 concentration. A weaker correlation was observed between oxygen or slurry concentration and removal efficiency. Finally several solid oxides were found to be effective additives for enhancing mercury capture in wet scrubbers.     

The organic composition of diesel particulate matter, diesel fuel and engine oil of a non-road diesel generator

Diesel-powered equipment is known to emit significant quantities of fine particulate matter to the atmosphere. Numerous organic compounds can be adsorbed onto the surfaces of these inhalable particles, among which polycyclic aromatic hydrocarbons (PAHs) are considered potential occupational carcinogens. Guidelines have been established by various agencies regarding diesel emissions and various control technologies are under development. The purpose of this study is to identify, quantify and compare the organic compounds in diesel particulate matter (DPM) with the diesel fuel and engine oil used in a non-road diesel generator. Approximately 90 organic compounds were quantified (with molecular weight ranging from 120 to 350), which include alkanes, PAHs, alkylated PAHs, alkylbenzenes and alkanoic acids. The low sulfur diesel fuel contains 61% alkanes and 7.1% of PAHs. The identifiable portion of the engine oil contains mainly the alkanoic and benzoic acids. The composition of DPM suggests that they may be originated from unburned diesel fuel, engine oil evaporation and combustion generated products. Compared with diesel fuel, DPM contains fewer fractions of alkanes and more PAH compounds, with the shift toward higher molecular weight ones. The enrichment of compounds with higher molecular weight in DPM may be combustion related (pyrogenic).     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Monitoring atmospheric metal pollution: a review of the use of mosses as indicators

This article reviews the literatureon the use of mosses for monitoring atmospheric metalpollution. It discusses the nature of mosses, themechanisms for moss uptake of metals from the air andwet precipitation, the various forms in which mossesare used for this purpose, and cases in which mosseshave been used for monitoring local hot spots ofpollution, and regional patterns of metal pollution.Also highlighted are the questions of uptake of metalsfrom the substrates, interspecies differences, and acomparison of the effectiveness of mosses with otherindicator materials, among other issues.     

Influence of environmental parameters on the accuracy of nitrogen dioxide passive diffusion tubes for ambient measurement

Two studies at three sites in the UK provided confirmation that systematic positive bias in NO2 diffusion tube measurement occurred because of changes to "within-tube" chemistry, rather than eddy diffusion at the mouth of the tube. In the first study in Cambridge, UK, sampler overestimation for 1 and 2 week exposures was compared to corresponding time-averaged monitor measurements (NO-NO2-NOx, O3) and weather variables. Noninearity between sampler and monitor NO2 measurements was interpreted in terms of spatial and temporal variations in relative and absolute availability of NO, NO2 and O3 at the site. A maximum overestimation occurred for an exposure mean NO2/NOx approximately 0.5. The separate contributions of reduced NO2 photolysis and eddy diffusion were compared in Study II using samplers of two materials, acrylic and quartz, and of different lengths (40, 55, 71 and 120 mm) at three sites: Norwich background, Cambridge intermediate, London kerbside. For compared sites, NO2 measured by acrylic samplers was significantly higher than for equivalent quartz samplers. For quartz samplers [NO2]mean was only just above the monitor at Norwich and London; sampler/monitor NO2 = 1.04 (P = 0.59) and 1.01(P = 0.76), respectively. For acrylic samplers the order of [NO2]mean was 40 mm > 120 mm > 71 mm > or = 55 mm. Excepting 40 mm samplers, this accords with a chemical bias where co-diffusing NO and 03 molecules in longer tubes have more time to react to form excess NO2. Bias in 40 mm samplers is discussed. Eddy diffusion is negligible for standard samplers because [NO2]mean was equivalent for 55 mm and 71 mm acrylic samplers and close to monitor NO2 for 71 mm quartz tubes. Both studies showed that sampler accuracy was dependent on location. Significantly, overestimation was greatest (approximately 3-4 ppb) where the NO2 annual mean was approximately 20 ppb, close to the UK and EU air quality standard of 21 ppb.     

Assessing the Effects of Atmospheric Ethylene on Epinasty and Tuber Yield of Potato (Solanum Tuberosum L.) Near Polyethylene Manufacturing Plants

A multi-year programme was performed to assess the effects of atmospheric ethylene on potato (Solanum tuberosum L.) in the vicinity of polyethylene manufacturing plants. There was a strong temporal variation of the hourly ethylene concentrations measured close to the sources from 1982 through 1991. Growing seasonal means exceeded 12 g m^–3 ethylene, the threshold for phytotoxic effects under laboratory conditions. Young test plants of potato showed an epinastic response to enhanced levels of ethylene. This response was reversible and did not occur when atmospheric ethylene was not detected. Based on hourly observations for the growing seasons of 1984 through 1991, epinasty occurred on average during circa 5% of the growing season and varied from circa 1% in 1985 to circa 18% in 1991. At night, ethylene concentrations were higher and epinasty was more frequent than during daylight hours. The intermittent exposures to ethylene did not affect tuber yield for the growing seasons of 1982 through 1990. The occurrence of epinasty indicated that ethylene exposure levels in the vicinity of the industrial sources might be sufficiently high to affect sensitive plants.     

Degradability and Sediment Sorption of an Alcohol Polyglycol Ether Surfactant Putatively Useful for the Control of Red Swamp Crayfish in Rice Fields

This work reports studies of the degradation rates of a fattyalcohol polyglycol ether non-ionic surfactant, Genapol OXD-080, putatively useful for the control of red swamp crayfish (Procambarus clarkii Girard) in rice fields under laboratory and field conditions. The influence of temperature,sediment site specificity and sorption were taken into account.The degradation kinetics of the surfactant depends on the experimental conditions: type of inocula and temperature. Thedistribution of this chemical in aquatic systems was also examined. Genapol OXD-080 was removed into the sedimentsreadily after application, and sorption was considered the majorpath of removal from the water phase. Data suggest that furtherstudies are required regarding the effects of Genapol OXD-080 in aquatic organisms resident in rice fields, in parallelwith the development of technologies related with the use ofsurfactants to control P. clarkii populations.     

Optimization of a multielement sequential extraction method employing an experimental design approach for metal partitioning in soils and sediments

The optimisation of a simple multielement extraction method employing an experimental design approach is described. The method uses centrifugation to pass one extractant solution at varying pH through a contaminated soil sample. The nature and concentration of the acid, rate of centrifugation and time, number of sequential leachates and the ratio of extractant volume: sample weight have been studied in order to obtain the optimum conditions for extraction. A fractional factorial experimental design was performed, and the results were used to identify significance which was then evaluated by carrying out a central composite experimental approach. Once optimum conditions had been obtained, sequential leaches were analysed by ICP-AES and chemometrics were employed to identify the composition of each component. Comparisons have been made with previous studies and tentative assignments, based on well defined separated fractions and percentage compositions for individual elements, used to identify the different physico-chemical components in the sample.