Rare Elements Electrochemistry: The Development of a Novel Electrochemical Sensor for the Rapid Detection of Europium in Environmental Samples Using Gold Electrode Modified with 2-pyridinol-1-oxide.

This work presents for the first time the electrochemical determination of europium using cyclic voltammetry at gold electrodes modified with 2-pyridinol-1-oxide. A well-defined oxidation peak was observed in cyclic voltammetry as a result of the oxidation of the europium at ∼1100 mV in phosphate buffer at pH 7.0. The peak current increased linearly with the increase of concentration of the europium over the range from 1 to 80 µM and detection limit (based on 3-sigma) and quantification were found to be 0.3 and 0.549 µM, respectively. The analytical utility of the developed protocol was evaluated by performing the detection of the europium in river water. Europium is also linear over the concentration range 10 to 150 µM. (I(p)/µA = 0.7239x + 108.19, R(2) = 0.9981 and n = 9) with a detection limit of 6.5 µM (based on 3-sigma). This simple and effective protocol exhibited good sensitivity, precision and reliability towards the detected analyte.

LED-controlled tuning of ZnO nanowires' wettability for biosensing applications.

BACKGROUND: Wettability is an important property of solid materials which can be controlled by surface energy. Dynamic control over the surface wettability is of great importance for biosensing applications. Zinc oxide (ZnO) is a biocompatible material suitable for biosensors and microfluidic devices. Nanowires of ZnO tend to show a hydrophobic nature which decelerates the adhesion or adsorption of biomolecules on the surface and, therefore, limits their application. METHODS: Surface wettability of the ZnO nanowires can be tuned using light irradiation. However, the control over wettability using light-emitting diodes (LEDs) and the role of wavelength in controlling the wettability of ZnO nanowires are unclear. This is the first report on LED-based wettability control of nanowires, and it includes investigations on tuning the desired wettability of ZnO nanowires using LEDs as a controlling tool. RESULTS: The investigations on spectral properties of the LED emission on ZnO nanowires' wettability have shown strong dependency on the spectral overlap of LED emission on ZnO absorption spectra. Results indicate that LEDs offer an advanced control on dynamically tuning the wettability of ZnO nanowires. CONCLUSION: The spectral investigations have provided significant insight into the role of irradiating wavelength of light and irradiation time on the surface wettability of ZnO nanowires. This process is suitable to realize on chip based integrated sensors and has huge potential for eco-friendly biosensing and environmental sensing applications.

Evaluations of combined zebrafish (Danio rerio) embryo and marine phytoplankton (Diacronema lutheri) toxicity of dissolved organic contaminants in the Ythan catchment, Scotland, UK.

A wide variety of organic contaminants including pesticides, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) have previously been detected in surface waters in the river Ythan catchment, North East Scotland UK. While the concentrations detected were below Water Framework Directive Environmental Quality Standards (WFD-EQSs) environmental exposures to the diverse mixtures of contaminants, known and unknown, may pose chronic and/or sublethal effects to non target organisms. The present study assessed the embryo and algal toxicity potential of freely dissolved organic contaminants from the Ythan catchment using silicone rubber passive sampling devices (SR-PSDs) and miniaturised bioassay techniques. Zebrafish (Danio rerio) embryos and marine phytoplankton species (Diacronema lutheri) were exposed to extracts from SR-PSDs deployed at different locations along the river Ythan and an undeployed procedural blank. Statistically significant developmental and algal toxicities were measured in all tests of extracts from deployed samples compared with the procedural blanks. This indicates environmental exposure to, and the combined toxicity potential of, freely dissolved organic contaminants in the catchment. The present and previous studies in the Ythan catchment, coupling SR-PSDs and bioassay techniques, have both helped to understand the interactions and combined effects of dissolved organic contaminants in the catchment. They have further revealed the need for improvement in the techniques currently used to assess environmental impact.

Silicone rubber passive samplers for measuring pore water and exchangeable concentrations of polycyclic aromatic hydrocarbons concentrations in sediments.

The use of a silicone rubber passive sampler for the assessment of the availability of lipophilic organic contaminants in sediments is described. The passive sampler accumulated polycyclic aromatic hydrocarbons (PAHs) from sediments with an equilibration time of 20 days for most PAHs. The method was used to measure the free dissolved concentrations in pore water of 30 PAHs (parent and alkylated), their water exchangeable concentrations and sediment-water partition coefficients in field sediments from a Scottish sea loch that supports fish farming. Fluoranthene and pyrene dominated the PAH concentration composition in the pore waters. The water exchangeable concentration reflected the pyrogenic pollution pattern found in the sediments and indicated that a proportion of the PAHs were not available for exchange with the aqueous phase. Strong linear relationships between organic carbon normalised sediment-water partition coefficients (logK(oc)) and corresponding octanol-water partition coefficients of PAHs were obtained. The logK(oc) values obtained are on average, 0.6 log units higher than literature values commonly used in sediment risk assessments, consequently direct measurements of logK(oc) in field sediments should be used to improve the reliability of risk assessments.

Occurrence and potential combined toxicity of dissolved organic contaminants in the Forth estuary and Firth of Forth, Scotland assessed using passive samplers and an algal toxicity test.

As an alternative procedure to conventional water quality assessment, the presence and combined toxicity of dissolved organic contaminants in water at five sites in the Forth estuary and the Firth of Forth, Scotland, United Kingdom was investigated using silicone rubber passive sampling devices (SR-PSDs) and an algal growth inhibition bioassay. SR-PSDs were deployed in water at the five sites for ~2 months. Following retrieval, extracts from the deployed SR-PSDs were assessed for both algal growth inhibition and the occurrence of a wide range of organic contaminants, including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and a variety of plant protection products (PPPs; commonly referred to collectively as 'pesticides'). The 72 h algal growth inhibition test was performed using a native marine phytoplankton (Diacronema lutheri) in 24 well microplates. Freely dissolved (e.g. bioavailable) concentrations of PAHs and PCBs were determined using performance reference compounds (PRCs). The algal toxicity tests exhibited varied effects at the five sites indicating the presence of, and exposure to, phytotoxic compounds and their potential toxicity in the Forth. The individual and total dissolved concentrations of 40 PAHs and 32 PCBs measured in the study were relatively low and showed input of petrogenic, atmospheric and sewage related sources. Several pesticides of diverse polarities were identified in the water suggesting sources from both riverine input and direct discharges. The study thus illustrates the value of combining bioassays and chemical analysis (with effective sampling technique) for a realistic and rapid assessment of organic contaminants in the aquatic environment.

Identification of selected organic contaminants in streams associated with agricultural activities and comparison between autosampling and silicone rubber passive sampling.

This study evaluates the potential of silicone rubber passive sampling devices (SR-PSDs) as a suitable alternative to automatic water samplers (autosamplers) for the preliminary identification of a wide range of organic contaminants in freshwater systems. The field performance of SR-PSDs deployed at three sites on two streams of an agricultural catchment area in North East (NE) Scotland, United Kingdom (UK) was assessed concurrently with composite water samples collected from two of the sites using autosamplers. The analytical suite consisted of selected plant protection products (PPPs; commonly referred to collectively as 'pesticides'), including 47 pesticides and a separate sub-category of 22 acid/urea herbicides. Of these, a total of 54 substances, comprising 46 pesticides and 8 urea herbicides were detected in at least one of the SR samplers. All but 6 of these SR-PSD detected substances were quantifiable. By comparison, a total of 25 substances comprising 3 pesticides and 22 acid/urea herbicides were detected in the composite water samples, of which only 8 acid/urea herbicides were quantifiable. The larger number and chemical classes of compounds detected and quantified via passive sampling reflect the lower limits of detection achieved by this device when compared to autosamplers. The determination of dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) added to the information on contaminant pressures at each site, allowing assessment of the reliability of SR-PSDs in freshwater systems and the identification of possible contaminant sources. The study demonstrated the utility of SR-PSDs for detecting and semi-quantifying low concentrations of analytes, including those which hitherto have not been measured in the catchment area and also some pesticides that are no longer approved for agricultural use in the UK and EU. The SR-PSD approach can thus provide a better understanding and clearer picture of the use and presence of organic contaminants within catchments.

Investigating the significance of dissolved organic contaminants in aquatic environments: coupling passive sampling with in vitro bioassays.

We investigated the feasibility of coupling passive sampling and in vitro bioassay techniques for both chemical and ecotoxicological assessment of complex mixtures of organic contaminants in water. Silicone rubber passive sampling devices (SR-PSDs) were deployed for 8-9 weeks in four streams and an estuary of an agricultural catchment in North East (NE) Scotland. Extracts from the SR-PSDs were analysed for freely dissolved hydrophobic organic contaminants (HOCs) and screened for wide range of pesticides. The total concentrations of dissolved PAHs (∑PAH(40), parent and branched) in the water column of the catchment varied from 38 to 69 ng L(-1), whilst PCBs (∑PCB(32)) ranged 0.02-0.06 ng L(-1). A number and level of pesticides and acid/urea herbicides of varying hydrophobicity (logK(OW)s ~2.25 to ~5.31) were also detected in the SR extracts, indicating their occurrence in the catchment. The acute toxicity and EROD induction potentials of SR extracts from the study sites were evaluated with rainbow trout liver (Oncorhynchus mykiss; RTL-W1) cell line. Acute cytotoxicity was not observed in cells following 48 h exposure to the SR extracts using neutral red uptake assay as endpoint. But, on a sublethal level, for every site, statistically significant EROD activity was observed to some degree following 72 h exposure to extracts, indicating the presence of compounds with dioxin-like effect that are bioavailable to aquatic organisms in the water bodies of the catchment. Importantly, only a small fraction of the EROD induction could be attributed to the PAHs and PCBs that were determined. This preliminary study demonstrates that the coupling of silicone rubber passive sampling techniques with in vitro bioassays is feasible and offers a cost effective early warning signal on water quality deterioration.

Application of silicone rubber passive samplers to investigate the bioaccumulation of PAHs by Nereis virens from marine sediments.

The availability of polycyclic aromatic hydrocarbons (PAHs) from marine sediments to the ragworm (Nereis virens) was studied. Concentrations of PAHs in pore waters were determined using silicone rubber passive samplers. Calculated bioconcentration factors confirmed that partitioning of PAHs between the lipid phase of the polychaetes and pore water is a passive process. Low biota-sediment accumulation factors (BSAF) calculated using total sediment concentration suggested a fraction of the total PAH burden in the sediment may be strongly sorbed to organic carbon and not available to the polychaete. Organic carbon normalised concentrations of the potentially exchangeable fractions of contaminants and freely dissolved concentrations (measured using silicone rubber samplers) provide a better description of the observed bioaccumulation by the ragworms. These data indicate that the concept of availability should be included in environmental risk assessments based upon equilibrium partitioning models, and that silicone rubber samplers can provide the necessary information for these models.

Variables to be considered when assessing the photocatalytic destruction of bacterial pathogens.

The current study sought to assess the importance of three common variables on the outcome of TiO(2) photocatalysis experiments with bacteria. Factors considered were (a) ability of test species to withstand osmotic pressure, (b) incubation period of agar plates used for colony counts following photocatalysis and (c) chemical nature of suspension medium used for bacteria and TiO(2). Staphylococcus aureus, Escherichia coli, Salmonella ser. Typhimurium and Pseudomonas aeruginosa were found to vary greatly in their ability to withstand osmotic pressure, raising the possibility that osmotic lysis may be contributing to loss of viability in some photocatalytic disinfection studies. Agar plate incubation time was also found to influence results, as bacteria treated with UV light only grew more slowly than those treated with a combination of UV and TiO(2.) The chemical nature of the suspension medium used was found to have a particularly pronounced effect upon results. Greatest antibacterial activity was detected when aqueous sodium chloride solution was utilised, with approximately 1 x 10(6) CFU mL(-1)S. aureus being completely killed after 60 min. Moderate activity was observed when distilled water was employed with bacteria being killed after 2h and 30 min, and no antibacterial activity at all was detected when aqueous tryptone solution was used. Interestingly, the antibacterial activity of UV light on its own appeared to be very much reduced in experiments where aqueous sodium chloride was employed instead of distilled water.

Passive sampling: partition coefficients for a silicone rubber reference phase.

Silicone rubber sheeting can be used as a passive sampling device for hydrophobic organic contaminants in the environment to determine the available concentrations in water and sediments. Reliable sampler-water partition coefficients are required to determine the sampling rates and the dissolved contaminant concentrations in water and in sediment pore water. Log partition coefficients (logK(sr,w)) for silicone rubber-water have been estimated for 32 polycyclic aromatic hydrocarbons (PAHs), 2 deuterated PAH analogues and 32 chlorobiphenyls (CBs) using the cosolvent method, with methanol as cosolvent. Strong linear relationships were found with literature values for the corresponding log octanol-water partition coefficients (logK(ow)) for both CBs and PAHs, confirming that partitioning into the silicone rubber is strongly determined by the hydrophobicity of the compounds, which suggests logK(ow) is a good predictor of logK(sr,w) and that absorption is the main mechanism for accumulation of analytes into the silicone rubber polymer.

Description and evaluation of a sampling system for monitoring hydrocarbons in sediments.

A composite random sampling design was used to estimate the concentrations of hydrocarbons in sediments from two near-shore areas of Scotland (Firth of Clyde and Firth of Forth). The aim of this work was to estimate a mean value for each parameter in these areas, and to determine whether this can be done with more thorough coverage (better representation), better precision and less variance at lower analytical cost through a composite random sampling scheme rather than a simple random sampling scheme, and thereby contribute to the re-design of the UK National Marine Monitoring Programme (NMMP), re-named the UK Clean Seas Environmental Monitoring Programme (CSEMP) in 2006. Samples were collected using a simple random sampling design during 2005. All sediment samples were analysed for their particle size distribution and total organic carbon (TOC). All sediments were analysed for polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. The concentrations of PAHs and n-alkanes in the study areas are described, and sources of PAHs were investigated through the PAH distributions and n-alkane profiles. Individual sediment samples from each area were combined to give a series of composite sub-samples, each comprised of 5 individual sediment samples. These composite samples were re-analysed for the same parameters as the individual samples. Mean total PAH (2- to 6-ring parent and branched) concentrations, based on the individual original sediment samples collected through simple random sampling, were 1858 microg kg(-1) dry weight (SE = 196 microg kg(-1) dry weight, n = 25) and 532.4 microg kg(-1) dry weight (SE = 59 microg kg(-1) dry weight, n = 25) in the Clyde and Forth, respectively. Mean total PAH concentrations of the composite samples were 1745 microg kg(-1) dry weight (SE = 121.0 microg kg(-1) dry weight, n = 5) in the Clyde and 511.6 microg kg(-1) dry weight (SE = 37.4 microg kg(-1) dry weight, n = 5) in the Forth. No significant differences were found between the mean PAH concentrations from the two sampling designs. This study demonstrated that the composite random sampling design gave a mean value with less variance than the simple random sampling design, at significantly reduced analytical effort (and cost).

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production.

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.