Factor analysis and linear regression model (LRM) of metal speciation and physico-chemical characters of groundwater samples

An approach is described for viewing the interrelationship between different variables and also tracing the sources of pollution of groundwater of north Chennai (India). The data set of 43 variables which include major ions, minor ions and trace metal speciation (Cu, Pb, Cd and Zn) collected during the pre-monsoon and post-monsoon seasons of the year 2000–2001, was subjected to R-mode factor analysis to comprehend the distribution pattern of the said variables. It was found that first factor measures salinity and hardness which explained 19.12% of the total variance (comprised of variables EC, TDS, Na⁺, K⁺, Ca²⁺, Mg²⁺, total hardness, Cl⁻ and SO₄ ²⁻) during pre-monsoon, while it was 25.08% during post-monsoon. The second and third factors were attributed to speciation of zinc and copper ions during both pre-monsoon and post-monsoon. Although there were two more factors, loaded with speciation parameters of lead and cadmium, the variance of them were less than 10%. From this study it is seen that sea water intrusion, municipal solid waste disposal are the identified sources of component of pollution. The importance of metal ions is taking a secondary role and the anthropogenic origin-industrial activity, is the reason in the evaluation of pollution status as they come in the second, third, fourth and fifth factors. As the trace metal speciation was grouped in separate factors, linear regression model (LRM) with correlation analysis was applied to check its validity for prediction of speciation and to apply LRM for rapid monitoring of water pollution.     

Bromate analysis in groundwater and wastewater samples

Bromate (BrO(3)(-)) is a disinfection by-product formed during ozonation of potable water supplies containing bromide (Br(-)). Bromate has been classed by the World Health Organisation as a 'possible human carcinogen', leading to implementation of 10-25 microg L(-1)(as BrO(3)(-)) drinking water limits in legislative areas including the United States and European Union. Techniques have been developed for bromate analysis at and below regulatory limits, with Ion Chromatography (IC) coupled with conductivity detection (IC-CD), post-column reaction and ultra-violet (UV) detection (IC-PCR), or inductively coupled plasma-mass spectrometry detection (IC-ICPMS) in widespread use. The recent discovery of bromate groundwater contamination in a UK aquifer has led to a requirement for analysis of bromate in a groundwater matrix, for environmental monitoring and development of remediation strategies. The possibility of bromate-contaminated water discharge into sewage treatment processes, whether accidental or as a pump-and-treat strategy, also required bromate analysis of wastewater sources. This paper summarises techniques currently available for trace bromate analysis in potable water systems and details studies to identify a methodology for routine analysis of groundwater and wastewater samples. Strategies compared were high performance liquid chromatography (HPLC) with direct UV or PCR/UV detection, IC-CD, IC-PCR, and a simple spectrophotometric technique. IC-CD was the most cost-effective solution for simultaneous analysis of bromate and bromide within groundwater samples, having a 5 microg L(-1) detection limit of both anions with limited interference from closely-eluting species. Wastewater samples were successfully analysed for bromate only using HPLC with PCR/UV detection, with detection limits below 20 microg L(-1)(as BrO(3)(-)) and low interference. HPLC with direct UV detection was unsuitable for bromate analysis within the concentration range 50-5000 microg L(-1) which was required for this project, but column choice was shown to be a major factor in determining limits of detection. Spectrophotometry could not reproducibly determine bromate concentration, although the technique showed promise as a quick field method for high-level groundwater bromate analysis.     

The analysis of monitoring data with the aid of time-series analysis

Methods derived from time-series analysis are proposed for processing monitoring data. The necessity for the use of these methods is demonstrated. In a case study time-series analysis was applied to assess the impact of the closure of the Grevelingen estuary (S. W. Netherlands) in 1971 on a local wintering population of Oystercatchers (Haematopus ostralegus) in the adjacent Oosterschelde estuary.Communication No. 328 of the Delta Institute for Hydrobiological Research.     

The distribution of octachlorostyrene (OCS) in environmental samples from Europe

Although octachlorostyrene (OCS) was never used as a commercial product, it may be produced during incineration and combustion processes involving chlorinated compounds. Its environmental spreading was evaluated through the analysis of several representative samples. OCS could not be measured in soil samples collected from urban and rural areas or sediments, but was present (up to 5.41 ng/g dry weight) in industrial soil collected near chemically polluted areas. For aquatic biota samples, the OCS concentrations in freshwater mussels ranged from <0.01 ng/g wet weight (ww) to 0.18 ng/g ww (mean 0.06 ng/g ww) and similar levels could be measured in 11 freshwater fish species from Belgium and Romania. A higher OCS contamination level was found in shrimps (mean 0.08 ng/g ww) compared to marine fish (mean 0.02 ng/g ww for bib and 0.01 ng/g ww for sole and whiting, respectively). OCS could also be measured in 19 harbour porpoise (Phocoena phocoena) liver samples with a mean value of 1.90 ng/g ww. According to these data, it could be computed that the biomagnification factor for OCS was one order of magnitude lower than that of HCB in the fish-porpoise food chain. The mean OCS concentrations in blue tits (Parus caeruleus) eggs and great tits (Parus major) adipose tissue were 1.24 ng/g ww and 3.24 ng/g ww, respectively. OCS could be measured in different tissues of hedgehog (Erinaceus europaeus), with the highest concentrations found in adipose tissue (mean 0.34 ng/g ww) and liver (mean 0.39 ng/g ww). In contrast, only low concentrations of OCS could be measured in human adipose tissue (up to 0.38 ng/g ww) and liver (up to 0.05 ng/g ww), while it could not be detected in human brain or lung. The relationship between the concentrations of OCS and HCB was also discussed for each species.     

Multi-element geochemical analysis of snow samples: Use of discriminant analysis in interpreting the results

This paper records the concentrations of major and trace elements determined from snow samples collected during a comprehensive survey undertaken in the Scottish Highlands during the winter and spring period of 1987. The configuration of calculated back-trajectories allowed the samples to be categorized into one of five geographical sectors. Discriminant analysis was used to check the validity of these calculations, to isolate potentially deviant samples, and to predict the possible source of one sample whose back-trajectory could not be computed with confidence. Limitations of the statistical method are discussed, but we conclude that the technique justifies more use by environmental scientists involved in the evaluation of data.     

Factor analysis of essential and toxic elements in human placentas from deliveries in arctic and subarctic areas of Russia and Norway

Concentrations in human placenta of 11 essential elements (P, Ca, Mg, Cu, S, Na, Fe, Zn, K, Se, Mn) and 5 toxic elements (Ba, Sr, Pb, Ni, Cd) are compared for each of two arctic communities in eastern Norway and western Russia, and for another in each country located at more southerly latitudes. All but Mg, Fe, P and K were present in higher concentrations in the Russian study group. The observed inter-element correlations are reflected by the four major factors identified in a principal component analysis. The total variation explained was 67.3%, of which more than half (35.3%) was contributed by Factor 1. P, Ca, Mg, Ba, Sr, Pb, and Ni were major contributors to this factor. The placental concentrations of these elements depended strongly on gestational age, increasing from about week 35 and peaking near weeks 39 and 40, and exhibited skewed frequency distributions and a dependence on maternal smoking. The gestational-dependent mineralization of the placenta is interpreted to reflect the deposition of metal phosphates coinciding with smoking-induced tissue damage. The loadings of the remaining three factors are reviewed in the context of common uptake mechanisms, similar biochemistries and unique transport pathways. The inter-element relationships and grouping of the elements observed should constitute a scientific base for the use of placenta composition in environmental monitoring and epidemiological studies.     

Ko method of quantification in neutron activation analysis as applied to environmental samples

The _Ko factor method in neutron activation analysis adopts all the principles of comparator method and can be used for the rapid determination of elemental comcentrations during routine monitoring of environmental samples. The method necessiates the use of same in-pile conditions, such as irradiation time, irradiation position and the type of neutron spectrum, for which the factors have been generated. The _{K_o} factors were estimated for various elements of environmental importance for three irradiation positions of Apsara Reactor at Bhabha Atomic Research Centre. Standard reference materials of soil and coal were used for all the elements except for Hg for which HgCl₂ was used. The concentration of the elements determined using these factors in a flyash standard reference material revealed good agreement within 10% of the certified values. The efficacy of the method compared well with that of specific element comparator method as revealed by the elemental concentrations obtained by both the techniques.     

Uncertainty Assessment of Voc Emissions from Paint in the Netherlands Using the Nusap System

We demonstrate an innovative approach to uncertainty assessment known as the NUSAP system, to assess qualitative and quantitative uncertainty for the case of emissions of volatile organic compounds (VOC) from paint in The Netherlands. Using expert elicitation, we identified key sources of error, critical assumptions, and bias in the monitoring process. We assessed pedigree and probabilistic uncertainty of all input quantities. We used four pedigree criteria to assess the strength of the knowledge base: proxy representation, empirical basis, methodological rigour and degree of validation. Using Monte Carlo analysis, we assessed sensitivity and propagation of uncertainty. Results for sensitivity and pedigree were combined in a NUSAP Diagnostic Diagram, which effectively highlighted the assumption for VOC percentage of imported paint as the weakest spot in the monitoring of VOC emissions. We conclude that NUSAP facilitates systematic scrutinization of method and underlying assumptions and structures creative thinking on sources of error and bias. It provides a means to prioritise uncertainties and focus research efforts on the potentially most problematic parameters and assumptions, at the same time identifying specific weaknesses in the knowledge base. With NUSAP, nuances of meaning about quantities can be conveyed concisely and clearly, to a degree that is not possible with statistic methods only.     

The effect of changes to the method of estimating the pollen count from aerobiological samples

Pollen data have been recorded at Novi Sad in Serbia since 2000. The adopted method of producing pollen counts has been the use of five longitudinal transects that examine 19.64% of total sample surface. However, counting five transects is time consuming and so the main objective of this study is to investigate whether reducing the number to three or even two transects would have a significant effect on daily average and bi-hourly pollen concentrations, as well as the main characteristics of the pollen season and long-term trends. This study has shown that there is a loss of accuracy in daily average and bi-hourly pollen concentrations (an increase in % ERROR) as the sub-sampling area is reduced from five to three or two longitudinal transects. However, this loss of accuracy does not impact on the main characteristics of the season or long-term trends. As a result, this study can be used to justify changing the sub-sampling method used at Novi Sad from five to three longitudinal transects. The use of two longitudinal transects has been ruled out because, although quicker, the counts produced: (a) had the greatest amount of % ERROR, (b) altered the amount of influence of the independent variable on the dependent variable (the slope in regression analysis) and (c) the total sampled surface (7.86%) was less than the minimum requirement recommended by the European Aerobiology Society working group on Quality Control (at least 10% of total slide area).     

Platinum concentrations in Danish air samples determined by instrumental neutron activation analysis

Platinum, gold and calcium concentrations of 20 samples of airborne dust collected at two sampling sites between 1995 and 1997 in the city of Copenhagen, which suffers from heavy traffic, were determined by instrumental neutron activation analysis (INAA). INAA of platinum using the 199Au daughter of 199Pt was performed. Two interferences on the INAA of platinum were removed by calculations. The spectral interference on 199Au from the 47Sc daughter of 47Ca was removed by separating the 157-161 keV doublet peak into its components by calculating the counts due to 47Sc from the counts of the parent 47Ca. The contribution of 197Au to 199Au by two neutron absorption was corrected for using the ratio 198Au/199Au in a pure Au standard. From the INAA results, high platinum concentrations are present in air in the range 0.25-2.74 ng m-3 and gold concentrations in the range 0.10-1.96 ng m-3.     

A comparison of X-ray fluorescence and wet chemical analysis of air filter samples from a scrap lead smelting operation

Personal and area air samples were taken at a scrap lead smelter operation in a bullet manufacturing facility. Samples were taken using the 37-mm styrene-acrylonitrile closed-face filter cassette (CFC, the current US standard device for lead sampling), the 37-mm GSP or "cone" sampler, the 25-mm Institute of Occupational Medicine (IOM) inhalable sampler, and the 25-mm Button sampler (developed at the University of Cincinnati). Polyvinylchloride filters were used for sampling. The filters were pre- and post-weighed, and analyzed for lead content using a field-portable X-ray fluorescence (XRF) analyzer. The filters were then extracted with dilute nitric acid in an ultrasonic extraction bath and the solutions were analyzed by inductively coupled plasma optical emission spectroscopy. The 25-mm filters were analyzed using a single XRF reading, while three readings on different parts of the filter were taken from the 37-mm filters. The single reading from the 25-mm filters was adjusted for the nominal area of the filter to obtain the mass loading, while the three readings from the 37-mm filters were inserted into two different algorithms for calculating the mass loadings, and the algorithms were compared. The IOM sampler was designed for material collected in the body of the sampler to be part of the collected sample as well as that on the filter. Therefore, the IOM sampler cassettes were rinsed separately to determine if wall-loss corrections were necessary. All four samplers gave very good correlations between the two analytical methods above the limit of detection of the XRF procedure. The limit of detection for the 25-mm filters (5 microg) was lower than for the 37-mm filters (10 microg). The percentage of XRF results that were within 25% of the corresponding ICP results was evaluated. In addition, the bias from linear regression was estimated. Linear regression for the Button sampler and the IOM sampler using single readings and the GSP using all tested techniques for total filter loading gave acceptable XRF readings at loadings equivalent to sampling at the OSHA 8-hour Action Level and Permissible Exposure Limit. However, the CFC only had acceptable results when the center reading corrected for filter area was used, which was surprising, and may be a result of a limited data set. In addition to linear regression, simple estimation of bias indicated reasonable agreements between XRF and ICP results for single XRF readings on the Button sampler filters, (82% of the individual results within criterion), and on the IOM sampler filters (77% or 61%--see text), and on the GSP sampler filters using the OSHA algorithm (78%). As a result of this pilot project, all three samplers were considered suitable for inclusion in further field research studies.     

Geostatistical analysis of Palmerton soil survey data

This paper presents a literature review focused on predictive technique audits, one of the types of audit considered to have the greatest potential role in improving environmental impact assessment practice. The literature review is limited to US literature with the exception of a few UK audits, one undertaken by Tomlinson at the University of Aberdeen. The authors are, however, aware that literature from other countries exists on this subject, for example from Canada and South Africa.In the review, predictive technique audits performed for or by the US Bureau of Land Management, the Electric Power Research Institute, the US Nuclear Regulatory Commission, the US Corps of Engineers, together with the Wisconsin Power Plant Impact Study are described. In addition, articles describing the auditing of models designed to predict environmental change are reviewed, before details of auditing activity in the UK are presented.     

Environmental Monitoring in The Netherlands: Past Developments and Future Challenges

During the past three decades environmental monitoringsystems covering an immense variety of environmentalproblems emerged rapidly throughout the world. In The Netherlands the entire spectrum of monitoring systemsis present. Their development is especially interesting because of the Dutch complex environmental landscape: a result of the combination of a natural setting with a high small-scale variation and an intense use of the available space by both industry and agriculture. This necessitates a well balanced environmental policy wherein monitoring ofboth environmental compartments and environmental policy itself plays an important role. In this article we focus on abiotic systems, whereby the development of monitoring will be related to that of environmental policy in general. Some general lines emerge: from quantity towards quality, from single pollutants towards environmentally harmful processes as a whole, and from a focus on human health and safety towards integrated environmental management. Because The Netherlands is a highly organized and highly educatedsociety, reacting fast and flexible to new problems, this progression has happened quickly. However, still much remains to be desired and flexibility not necessarily guarantees optimal routes of development. Paramount is the development of sophisticated and robust monitoring systems that truly support integrated environmental management. This asks forclear objectives based on solid scientific insights.     

Solid phase extractive preconcentration of silver from aqueous samples

N,N-dibutyl-N1-benzoylthiourea (DBBT) impregnated onto a polymeric matrix, Amberlite XAD-16 was prepared. The separation and enrichment of Ag(I) from solution was investigated. Effective extraction conditions were optimized in column methods prior to determination by atomic absorption spectrometry. The optimum pH range for quantitative adsorption is 2-5. Quantitative recovery of Ag was achieved by stripping with 1 mol L(-1) thiourea in 1 mol L(-1) HCl. The sorption capacity of resin is 0.115 mmol Ag+ g(-1) resin. The relative standard deviation and detection limit was 3.1% for 1 microg Ag+ mL(-1) solution and 0.11 microg L(-1), respectively. The method was used for the determination of silver in geological water samples.     

Statistical zonation of sediment samples using ratio matching and cluster analysis

A zonation technique for sediment samples based upon contaminant ratios of a series of samples is described. The technique is based on the fact that sediment samples of common origin will tend to have similar ratios of concentrations of trace pollutants such as heavy metals, PCBs, etc., despite dilution by variable amounts of inert materials such as silica or calcite. Comparison of these ratios between individual samples yields a matrix of similarity coefficients, which are then analyzed by a hierarchical agglomerative cluster analysis procedure. Sediment samples of similar origin will tend to group together in a single cluster, whereas samples influence by unique factors such as transport patterns or proximity to point source discharges will appear as separate individual clusters. The results of application of this methodology to Great Lakes samples from Hamilton Harbour and Port Hope are presented.     

Effect-based assessment of passive air samples from four countries in Eastern Europe

Although passive sampling has been previously used for the monitoring of volatile and semi-volatile contaminants in air, there are limited data on the use of this technique coupled with bioassays based on specific biological responses. Biological responses including those mediated by the aryl hydrocarbon (AhR) receptor as well as (anti-)estrogenicity and (anti-)androgenicity of samples from four Eastern European countries (Lithuania, Slovakia, Romania, and Serbia) were determined. To address the potential differences of specific toxic potencies of pollutant mixtures in ambient air in Eastern Europe, each country was characterized by a single more remote location that served to determine regional background conditions and one location in more urbanized and industrialized locations, which were defined as “impacted” areas. Besides samples from Lithuania, a significant gradient in concentrations of AhR-mediated potency from background and impacted localities was observed. Greatest potencies were measured in samples from impacted locations in Romania and Slovakia. Concentrations of polycyclic aromatic hydrocarbons (PAHs) that were quantified accounted for 3–33 % of the 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents determined by use of the bioassay. No significant estrogenic potency was detected but anti-estrogenic effects were produced by air from two background locations (Lithuania, Slovakia) and three impacted locations (Lithuania, Romania, and Serbia). Anti-androgenic potency was observed in all samples. The greatest anti-estrogenic potency was observed at the background location in Slovakia. Anti-estrogenic and anti-androgenic potencies of studied air samples were probably associated with compounds that are not routinely monitored. The study documents suitability of passive air sampling for the assessment of specific toxic potencies of ambient air pollutants.     

Assessment of elemental contaminants in water and fish samples from Aba river

The elemental contaminants in water and fish samples from Aba river were studied. The elements studied were Zn, Ni, As, Hg, Co and Mn. Three water samples and three samples of different fish species were collected from different locations in the river. The water and fish samples were analysed for elemental contaminants using Atomic Absorption Spectrophotometer (AAS). The elemental toxicants Zn and Mn were identified in appreciable amounts in fresh fish species namely, Lates niloticus and Oriochronis niloticus, of mean values 8.012 ppm and 0.861 ppm, respectively. The analysis also shows arsenic concentration of mean value 0.01 ppm in Lates niloticus. The analysis of frozen fish samples purchased from the Waterside market located near the river shows Ni and Hg levels of mean values 0.83 ppm and 0.02 ppm, respectively. The levels of elemental contaminants As, Zn, Hg and Mn from the water samples have mean values 0.082 ppm, 11.284 ppm, 0.201 ppm and 1.024 ppm, respectively. There are five industries that discharge waste products into Aba river. In view of this, there is a need to determine the level of pollution of the river, since the inhabitants depend on the river for their drinking water, fishing and other domestic uses. This study is aimed at determining the level of heavy metal toxicants in fish and water samples from the river. The effect of these elemental contaminants and the associated health hazards were examined.