ESTIMATION OF ERRORS IN ABSORBANCE RATIO MEASUREMENTS

Ratio measurements are commonly used to address a variety of analytical problems in environmental,forensic and pharmaceutical laboratories.In absorbance ratioing techniques,analytical chemists rely onthe spectral features of the analyte(s)of interest.The absorbances at two wavelengths are monitored andthe ratio of these two absorbances is computed.This ratio is then used to confirm the identity of theanalyte(s)of interest,the purity of a product or the overlap of chromatographic peaks.These decisionsoften have far-reaching consequences(e.g.the identification of the source,biogenic or petrogenic,ofhydrocarbons in biological tissues or water).Given the cost and the liabilities associated with suchdecisions,it is unfortunate that these ratios are seldom reported with any statistical confidence.Thepurpose of this study is to delineate the parameters that affect absorbance ratio measurements.Themodels that can be used to estimate the statistical confidence in these measurements are derived andevaluated experimentally.The results show that these models can estimate the relative standard deviationsin absorbance ratios accurately.They can also estimate the effect of signal-to-noise ratio and the choiceof wavelengths on the precision of absorbance ratios.     

The 1997/1998 mass mortality of corals: effects on fish communities on a Tanzanian coral reef

The abnormally high surface temperatures in the world's oceans during 1997/1998 resulted in widespread coral bleaching and subsequent coral mortality. An experiment was performed to study the effects of this coral mortality as well as the influence of the structural complexity on fish communities on a Tanzanian coral reef. Changes in fish communities were investigated on plots of transplanted corals after 88% of these corals had died. A distinct shift in fish community composition was found, although diversity was not affected. Fish abundance rose by 39% mostly due to an increase in herbivores, which seemed to benefit from enhanced algal growth on the dead corals. Fish abundance, species diversity and community composition were also strongly influenced by the structural complexity provided by the live and dead corals. This suggests that a coral reef can support abundant and diverse fish populations also after the corals have died as long as the reef structure is sustained.     

SEDIMENT TRANSPORT PROCESSES IN AGRICULTURAL WATERSHEDS

lINTR0DUCTI0NTheerosion,transportanddep0siti0nofsedimentinawatershedarepallofthenaturalsystemofwatershedprocesses.InanundistUrbedwatershed,s0ilsinuplandareasaregraduallyeroded,transportCdforsomedistanceandeventuallydepositedatlowereIevations.WhenwatershedsaredistUrbedbyhumanactivitiessuchasclearingofvegetation,urbaniZati0n,orotherchangesthataffectthelandscaPe,unstablechannelswithlocallyhighratesoferosion,transport,0rdepositionofsedimentoftenaretheresult.Theimpact0fer0sionisespeciallyhigh…     

Integrated biomarker assessment of the effects exerted by treated produced water from an onshore natural gas processing plant in the North Sea on the mussel Mytilus edulis

The biological impact of a treated produced water (PW) was investigated under controlled laboratory conditions in the blue mussel, Mytilus edulis. Mussel health status was assessed using an integrated biomarker approach in combination with chemical analysis of both water (with SPMDs), and mussel tissues. Acyl-CoA oxidase activity, neutral lipid accumulation, catalase activity, micronuclei formation, lysosomal membrane stability in digestive cells and haemocytes, cell-type composition in digestive gland epithelium, and the integrity of the digestive gland tissue were measured after 5 week exposure to 0%, 0.01%, 0.1%, 0.5% and 1% PW. The suite of biomarkers employed were sensitive to treated PW exposure with significant sublethal responses found at 0.01-0.5% PW, even though individual chemical compounds of PW were at extremely low concentrations in both water and mussel tissues. The study highlights the benefits of an integrated biomarker approach for determining the potential effects of exposure to complex mixtures at low concentrations. Biomarkers were integrated in the Integrative Biological Response (IBR/n) index.     

The atmospheric lead record preserved in lagoon sediments at a remote equatorial Pacific location: Palmyra Atoll, northern Line Islands

Anthropogenic lead (Pb) inputs to the atmosphere increased greatly over the past century and now dominate Pb supply to the oceans. However, the Pb content of sediments across the equatorial Pacific region is relatively unknown, and data exist only for deep sea sites where Pb deposition lags surface water inputs by up to a century. Here we present ICP-MS analyses of Pb of a core from a lagoon at Palmyra Atoll, northern Line Islands, that spans approximately the past 160 years. The non-bioturbated sediments of the euxinic lagoon, coupled with rapid rates of deposition, provide a unique fine-scale record of atmospheric Pb supply at a remote Pacific location. These first observations of historic Pb sedimentation in an atoll lagoon reveal a 63-fold increase in Pb flux to sediments during the past century and correlate directly with the North American consumption of leaded gasoline that began in 1926.     

A study on the mixing proportion in groundwater samples by using Piper diagram and Phreeqc model

Piper (1944) diagram has been the basis for several important interpretations of the hydrogeochemical data. As seen in this diagram, most natural waters contain relatively few dissolved constituents, with cations (metals or bases) and anions (acid radicles) in chemical equilibrium with one another. Apart from the facies representation, the composition of the mixed sample can be identified in terms of the composition of the parental solution. To bring out this advantage of the Piper diagram, a study was conducted in the Kalpakkam region of Tamilnadu, South India. By taking the geology and water table into consideration, two sample locations were selected as parent solution and third one as the mixture sample. All three samples were analyzed for calcium (Ca), magnesium (Mg), sodium (Na), potassium (K), chloride (Cl), sulphate (SO4) and phosphate (PO4) by Ion Chromatograph (Metrohm IC 861). HCO3 was determined by volumetric titration. The Piper diagram shows that parent solutions clustered towards Na-Mg-Ca-HCO3-Cl and Na-HCO3 facies, and the mixing sample belongs to Na-Mg-HCO3 facies. Phreeqc interac-tive (Ver 2.8) along with the original composition of the mixture sample was used to correlate the mixing proportion identified by the Piper diagram.     

Reservoir Quality Assessment of the Upper Permian Chhidru Formation,Salt and Surghar Ranges,Pakistan

The Late Permian succession of the Upper Indus Basin in northeastern Pakistan is represented by the carbonate-dominated Zaluch Group, which consists of the Amb, Wargal and Chhidru formations, which accumulated on the southwestern shelf of the Paleo-Tethys Ocean, north of the hydrocarbon-producing Permian strata of the Arabian Peninsula. The reservoir properties of the mixed clastic-carbonate Chhidru Formation (CFm) are evaluated based on petrography, using scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD) techniques. The diagenetic features are recognized, ranging from marine (isopachous fibrous calcite, micrite), through meteoric (blocky calcite-I, neomorphism and dissolution) to burial (poikilotopic cement, blocky calcite-II-III, fractures, fracture-filling, and stylolites). Major porosity types include fracture and moldic, while inter- and intra-particle porosities also exist. Observed visual porosity ranges from 1.5%–7.14% with an average of 5.15%. The sandstone facies (CMF-4) has the highest average porosity of 10.7%, whereas the siliciclastic grainstone microfacies (CMF-3) shows an average porosity of 5.3%. The siliciclastic mudstone microfacies (CMF-1) and siliciclastic wacke-packestone microfacies (CMF-2) show the lowest porosities of 4.8% and 5.0%, respectively. Diagenetic processes like cementation, neomorphism, stylolitization and compaction have reduced the primary porosities; however, processes of dissolution and fracturing have produced secondary porosity. On average, the CFm in the Nammal Gorge, Salt Range shows promise and at Gula Khel Gorge, Trans-Indus, the lowest porosity.     

TENSORIAL RESOLUTION:A DIRECT TRILINEAR DECOMPOSITION

Modern instrumentation in chemistry routinely generates two-dimensional(second-order)arrays of data.Considering that most analyses need to compare several samples,the analyst ends up with a three-dimensional(third-order)array which is difficult to visualize or interpret with the conventional statisticaltools.Some of these data arrays follow the so-called trilinear model,(?)These trilinear arrays of data are known to have unique factor analysis decompositions which correspondto the true physical factors that form the data,i.e.given the array (?),a unique solution can be found inmany cases for each order X,Y and Z.This is in contrast to the well-known second-order bilinear datafactor analysis,where the abstract solutions obtained are not unique and at best cannot be easilycompared with the underlying physical factors owing to a rotational ambiguity.Trilinear decompositions have had the disadvantage,however,that a non-linear optimization withmany parameters is necessary to reach a least-squares solution.This paper will introduce a method forreducing the problem to a rectangular generalized eigenvalue-eigenvector equation where the eigenbectorsare the contravariant form(pseudo-inverse)of the actual factors.It is shown that the method works wellwhen the factors are linearly independent in at least two orders(e.g.X_(jr),and Y_(jr) are full rank matrices).Finally,it is shown how trilinear decompositions relate to multicomponent calibration,curve resolutionand chemical analysis.     

THE PROBLEM OF ADEQUATE SAMPLE SIZE IN PATTERN RECOGNITION STUDIES:THE MULTIVARIATE NORMAL CASE

Because many pattern recognition techniques are predicated on the assumption of mutivariate normaldata,Monte Carlo simulation studies were performed to determine the number of samples that arenecessary to describe a multivariate normal population adequately.From these studies we have learnedthat hundreds of sainples are required.These results suggest that parametric procedures should only beused to analyze very large data sets.     

ENHANCING THE DECONVOLUTION OF NOISY CHROMATOGRAPHIC DATA BY JANSSON''S METHOD

In previous papers Jansson's method was found to be successful at deconvolving severely overlapped gaschromatographic peaks.In the most recent paper the method was evaluated with respect to quantitativeaceuracy,peak area and retention time repeatability.The problems associated with deconvolving noisydata and some alternatives which can improve the ability of Jansson's method to deconvolve noisy dataare discussed.These alternatives include presmoothing the data with a nine-point,third-order polynomialfilter and data reblurring.This paper will test these methods on peaks with various degrees of resolutionand signal-to-noise ratios.