Grady Hanrahan

Electrochemical sensors for environmental monitoring: design, development and applications

The advancement in miniaturization and microfabrication technology has led to the development of sensitive and selective electrochemical devices for field-based and in situ environmental monitoring. Electrochemical sensing devices have a major impact upon the monitoring of priority pollutants by allowing the instrument to be taken to the sample (rather than the traditional way of bringing the sample to the laboratory). Such devices can perform automated chemical analyses in complex matrices and provide rapid, reliable and inexpensive measurements of a variety of inorganic and organic pollutants. Although not exhaustive due to the vast amounts of new and exciting electrochemical research, this review addresses many important advances in electrochemical sensor design and development for environmental monitoring purposes. Critical design factors and development issues including analytical improvements (e.g. detection limits), microfabrication and remote communication are presented. In addition, modern environmental applications will be discussed and future perspectives considered.

Application of factorial and response surface methodology in modern experimental design and optimization

This article critically examines the use of factorial and response surface methodology in modern experimental design and optimization. A survey of important screening and optimization techniques in the literature since 2000 are presented. Current applications in biological, environmental and pharmaceutical analysis, food technology and industrial-related processes are examined.

Sampling, sample treatment and quality assurance issues for the determination of phosphorus species in natural waters and soils

Phosphorus is an important macronutrient and the accurate determination of phosphorus species in environmental matrices such as natural waters and soils is essential for understanding the biogeochemical cycling of the element, studying its role in ecosystem health and monitoring compliance with legislation. This paper provides a critical review of sample collection, storage and treatment procedures for the determination of phosphorus species in environmental matrices. Issues such as phosphorus speciation, the molybdenum blue method, digestion procedures for organic phosphorus species, choice of model compounds for analytical studies, quality assurance and the availability of environmental CRMs for phosphate are also discussed in detail.

Reduced inorganic phosphorus in the natural environment: significance, speciation and determination

It is commonly assumed that phosphorus occurs almost exclusively in the environment as fully oxidized phosphate (primarily H(2)PO(4)(-) and HPO(4)(2-), where the oxidation state of phosphorus is +V). Recent developments in the field of microbiology and research on the origin of life have suggested a possibly significant role for reduced, inorganic forms of phosphorus in bacterial metabolism and as evolutionary precursors of biological phosphate compounds. Reduced inorganic forms of phosphorus include phosphorus acid (H(3)PO(3), P(+III)), hypophosphorus acid (H(3)PO(2), P(+I)) and various forms of phosphides (P(-III)). Reduced phosphorus has been detected in anaerobic sediments, sewage treatment facilities and in industrial and agricultural processes. Microbiological evidence suggests a significant role for reduced phosphorus species in metabolic processes and raises interesting questions regarding the biogeochemistry of this nutrient in the environment. However, the paucity of data on the presence and cycling of reduced phosphorus compounds in the environment requires attention in order to elucidate the role of these compounds in natural systems. This paper discusses the significance of reduced phosphorus in the natural environment, its speciation and methods of detection.

Comparison of sample storage protocols for the determination of nutrients in natural waters

There have been several reports on storage protocols for the determination of nutrients in natural waters but each one has been limited to a particular sample matrix and they have reached different, matrix specific conclusions. The aim of this study was therefore to systematically apply the various recommended storage protocols to a range of natural water matrices. Samples from four contrasting sites in the UK, collected in late winter (February, 1999), were filtered and stored under different conditions (-80 degrees C, -20 degrees C, 4 degrees C and at 4 degrees C and -20 degrees C with 0.1% (v/v) chloroform) for up to 247 days prior to analysis. The sites were the River Frome in Dorset (a chalk stream catchment) and three sites from the Tamar Estuary (draining a non-chalk catchment) with salinities of 0.5 per thousand, 10 per thousand and 34 per thousand, Samples and controls were analysed for total oxidised nitrogen (TON) and filterable reactive phosphorus (FRP) using a segmented flow analyser with spectrophotometric detection. To investigate possible seasonal effects (particularly changes in biological and chemical matrix composition). a second sampling campaign was undertaken in early autumn (October, 1999). The results showed that the optimum storage conditions for the determination of TON and FRP were highly matrix dependent. with significant differences in FRP stability between the Frome and Tamar catchments (due to different calcium concentrations) and between samples of different salinities (due to different bacterial populations and/or dissolved organic matter). General guidelines for sample handling and storage are listed and matrix specific recommendations presented for samples rich in calcium and dissolved organic matter.

Flow Analysis Techniques for Spatial and Temporal Measurement of Nutrients in Aquatic Systems

Environmental Context.Eutrophication is a growing problem globally, and it has significant ecological and socio-economic consequences. Understanding the causes of eutrophication requires a knowledge of nutrient biogeochemistry in aquatic systems. Owing to the high spatial and temporal variability of nutrients in these systems, there is a need for autonomous in situ measurement techniques with rapid response and the ability to collect long-term data. Flow injection analysis is one technique that meets these demands. Abstract.Flow analysis offers a versatile and powerful approach to monitoring of the aquatic environment. The present review highlights the drivers for determining macro- and micro-nutrients in marine and fresh waters, and outlines the instrumental requirements for in situ instrumentation. The principles of flow analysis, specifically flow injection and derivative techniques, and the chemical bases for macro- and micro-nutrient detection are discussed, and key examples of suitable approaches are considered. The successful deployment of flow analysis nutrient monitoring systems for spatial and temporal measurements is illustrated by specific examples relating to surface transects, depth profiles and temporal deployments. Finally, the challenges and imperatives of research in this area are outlined.

Identification of Bacteria by Conjugated Oligoelectrolyte/Single-Stranded DNA Electrostatic Complexes

Electrostatic complexes containing a cationic conjugated oligoelectrolyte (COE) and fluorescein (FAM)-labeled single-stranded DNA (ssDNA) serve as the basis for identifying various bacteria. The approach involves the preparation of five COE/ssDNA(x)-FAM electrostatic complexes, which differ in the ssDNA composition and which provide different photoluminescence (PL) spectra as a result of different degrees of energy transfer efficiency from the COE to FAM. Changes in the PL spectra upon addition of the bacteria can be quantified, and the differential response from the five ssDNAs gives rise to a multicomponent array response that allows identification of the microorganism under investigation.

Detection of Geothermal Phosphite Using High Performance Liquid Chromatography

Little is known about the prebiotic mechanisms that initiated the bioavailability of phosphorus, an element essential to life. A better understanding of phosphorus speciation in modern earth environments representative of early earth may help to elucidate the origins of bioavailable phosphorus. This paper presents the first quantitative measurements of phosphite in a pristine geothermal pool representative of early earth. Phosphite and phosphate were initially identified and quantified in geothermal pool and stream samples at Hot Creek Gorge near Mammoth Lakes, California, using suppressed conductivity ion chromatography. Results confirmed the presence of 0.06 +/- 0.02 microM of phosphite and 0.05 +/- 0.01 microM of phosphate in a geothermal pool. In the stream, phosphite concentrations were below detection limit (0.04 microM) and phosphate was measured at 1.06 +/- 0.36 microM. The presence of phosphite in the geothermal pool was confirmed using both chemical oxidation and ion chromatography/mass spectrometry.

High temporal resolution field monitoring of phosphate in the River Frome using flow injection with diode array detection

The design and deployment of an in situ flow injection (FI) monitor for high temporal resolution monitoring of phosphate in the River Frome, Dorset, UK, is described. The monitor incorporates solenoid, self-priming micropumps for propulsion, solenoid-operated switching valves for controlling the fluidics and a miniature CCD spectrometer for full spectrum (200-1000 nm) acquisition and operates in a graphical programming environment. A tangential filtration unit is attached to the sample inlet line to remove suspended particulate matter and prevent blockage of the micropumps and valves. Detection (at 7 10 nm) is based on molybdenum blue chemistry with tin(II) chloride reduction. The detection limit is 0.67 muM PO4 and the linear range can be adjusted by using different wavelengths for detection. Pump noise is eliminated by subtraction of the signal at a non-absorbing wavelength (447 nm). Data from an intensive (sample every 30 min) field trial on the River Frome performed in October 2000 are presented, and the implications of the data for refining an export coefficient model for phosphorus from the catchment are discussed.

Computational Neural Networks Driving Complex Analytical Problem Solving

Neural network computing demonstrates advanced analytical problem solving abilities to meet the demands of modern chemical research. (To listen to a podcast about this article, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html .).