Estimating Trophic State Proportions of a Regional Lake Population: Are Larger Samples Always Better?

During the summers of 1991–1994, the Environmental Monitoringand Assessment Program (EMAP) sampled 344 lakes throughout thenortheastern United States using a proportional stratified sampling design based on lake size. Approximately one-quarter ofthe 344 lakes were sampled each year (4 years) for totalphosphorus to determine the proportion (and associated95% confidence intervals) of the northeast lake population 1ha (11,076 ± 1,699 lakes) that was in oligotrophic,mesotrophic, eutrophic, or heupereutropic (4 classes) conditionaccording to the total phosphorus criteria of the North AmericaLake Manegement Society. Estimates for the second, third, andfourth yr were developed as cumulative of the previous yrsamples and the current yr samples for the northeast as a wholeand for each of its three ecoregions (4 regions). New confidence intervals were computed for each cumulative yrcondition estimate. This produced a total (4 years × 4classes × 4 regions) of 64 cumulative yr tropic conditionestimates. Confidence intervals for 21% of these estimates didnot shorten with increased sample size. This phenomena raisedquestions about the accuracy of estimates based on cumulativesampling procedures. We explain why and how the phenomenon comesabout with both straight random and proportional randomsampling. Further, we present an example of the effects thisphenomenon has on lake tropic state condition estimates in thenortheastern United States.     

Chlorobiphenyl contaminants at Pladda and Garroch Head in the Firth of Clyde in relation to sewage sludge input

Sewage sludge dumped at Garroch Head in the Firth of Clyde contains significant quantities of chlorinated hydrocarbons, such as polychlorinated biphenyls (CBs). These compounds are lipophilic and resistant to degradation. They accumulate in the biota either from the water column or through the food chain, particularly in tissue with a high lipid content. Bottom dwelling fish, such as plaice, in the vicinity of the dump site will accumulate CBs from their environment. Eighteen of the 209 CBs were measured in plaice livers from the Garroch Head dump site and from Pladda, a site reasonably remote from the dump site but also in the Clyde, over a 7 year period prior to the cessation of dumping in December 1998. Concentrations of the congeners in the liver of fish caught at the dump site were, in general, higher than those in the liver of fish caught at Pladda. Concentrations in the plaice livers for the sum of 18 CBs ranged from 1611 to 8471 micrograms kg-1 lipid for Garroch Head samples and from 336.9 to 2635 micrograms kg-1 lipid for samples from Pladda. The data were evaluated using principal component analysis (PCA). Pattern analysis was undertaken by normalising to the recalcitrant CB 153. Livers from the dump site were found to have a higher proportion of the lower chlorinated CBs. CB patterns were similar at the Garroch Head dump site from year to year, but multivariate techniques showed that there were differences in pattern when normalised to CB 153.     

Preliminary studies of a fast screening method for polycyclic aromatic hydrocarbons in soil by using solvent microextraction-gas chromatography

Solvent microextraction (SME) was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from spiked and real environmental soil samples with different matrices. Soil sample was mixed with 7 mL of acetone and 14 mL of water to allow partitioning of the PAHs from the soil to the liquid phase. A 2 microL octane drop suspended from a microsyringe needle tip was then immersed into the stirred solution-soil mixture for extraction. After an 11 min extraction, the octane drop was withdrawn into the syringe and injected directly into the GC for identification and quantification. The whole analysis procedure took 27 min, with an extraction time of 11 min, and a GC separation time of 16 min. A second extraction could be undertaken whilst the GC is running, hence the GC run time currently limits the sample throughput. In this method, a small amount of organic solvent was used for the extraction process, which produced little waste. The limits of detection for lower molecular weight (< 230) PAHs range from 0.13 to 0.36 mg kg-1, and for higher molecular weight (> 250) PAHs are estimated to be between 0.5 and 1.0 mg kg-1, with RSD values generally under 20%. Due to the small volumes of organic solvent used, the consumable cost per extraction is only US$ 0.12. This is the first report of the application of SME to solid samples, and the first report of the use of SME for the analysis of PAHs.     

A ten channel fibre-optic device for distributed sensing of underground hydrocarbon leakage

With millions of fuel storage tanks and oil pipelines installed around the world, there is inevitably frequent leakage of potentially hazardous hydrocarbons. As many of these installations are below ground, it can often be many years before the extent of the leak is discovered. We have previously reported the development of a sensor for the detection of such subterranean leaks, using infrared reflectometry to interrogate a hydrocarbon sensitive membrane. However, a single sensor cannot provide any information about the flow rate or direction of the leak. This paper describes the extension of the technology to a multi-channel distributed sensing system, using optical fibres capable of distributing the sensors over large subterranean areas. Results are reported from the evaluation of the device, which consisted of monitoring the movement of different hydrocarbons (gasoline, diesel and insulating oil) through a vertical sand-filled vessel.     

Study of the relationships between bone lead levels and its variation with time and the cumulative blood lead index, in a repeated bone lead survey

The study aims were to: (i) investigate long term human lead metabolism by measuring the change of lead concentration in the tibia and calcaneus; and (ii) assess whether improved industrial hygiene was resulting in a slow accumulation of lead in an exposed workforce. 109Cd excited K X-ray fluorescence was used to measure tibia lead and calcaneus lead concentrations in 101 workers in a secondary lead smelter. 51 subjects had had similar bone lead measurements 5 years previously. Most of the other subjects had been hired since the first survey. Measurements of whole blood lead were available for the large majority of subjects. Tibia lead concentrations fell significantly (p<0.001) in the 51 subjects with repeated bone lead measurements, from a mean of 39 microg Pb (g bone mineral)(-1) to 33 microg Pb (g bone mineral)(-1). The change correlated negatively with the initial tibia lead concentration, producing an estimate for an overall half-life of 15 years, with a 95% confidence interval of 9 to 55 years. Adding continuing lead exposure and recirculation of bone lead stores to the regression models produced half-life estimates of 12 and 9 years, respectively, for release of lead from the tibia. The repeat subjects showed no net change in calcaneus lead (64 microg Pb (g bone mineral)(-1) initially, 65 microg Pb (g bone mineral)(-1) 5 years later). Subjects not measured previously had average lead concentrations of 15 microg Pb (g bone mincral)(-1) in the tibia and 13 microg Pb (g bone mineral)(-1) in the calcaneus. The rate of clearance of lead from the tibia (9 to 15 years) is towards the more rapid end of previous estimates. The lack of a significant fall in the calcaneus lead was surprising. Attempts should be made to repeat this observation. If confirmed, it would have implications for models of lead metabolism. The relatively low lead concentrations in the non-repeat subjects are reassuring. However, observation after a longer period of employment would be desirable.     

Detecting and characterising sources of persistent organic pollutants (PAHs and PCBs) in surface sediments of an industrialized area (harbour of Trieste, northern Adriatic Sea)

A sediment sampling based on a two-dimensional mapping was performed in the harbour of Trieste (northern Adriatic Sea), considering 28 sites exposed to pollutant inputs from harbour and industrial activities. Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in surface sediments, because these very persistent pollutants seem to be responsible for the depletion of benthic populations observed in this area. The correlation matrix indicates that PAHs and PCBs are non-correlated, and probably have different sources. Both cluster analysis performed on the sampling sites and graphical drawing of the PAH sediment contents make it possible to locate along the shoreline a band of more polluted sediments, clustered around a site facing a steelmaking factory, to be considered as the main source point for PAHs. The evaluation of phenanthrene to anthracene (P/AN) and fluoranthene to pyrene (FL/PY) ratios permits the assessment of the pyrolytic, industrial origin of these PAHs, rejecting a second possible source of hydrocarbons (i.e., an oil-pipeline terminal, situated near the steelmaking factory). Graphical drawing of the total PCB iso-concentrations reveals a different source-point for this other category of very persistent pollutants.     

Adsorption characteristics of a phenoxy acetic acid herbicide on activated carbon

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) by two powdered coal activated carbons was studied in aqueous solution. The modelling of the adsorption equilibrium showed that the adsorption of 2,4-D fitted a Langmuir isotherm. Adsorption was influenced by the activated carbon type, adsorbent concentration and solution characteristics. The adsorption was found to decrease with an increase in pH over the range 1.5-9. Maximum adsorption occurred at pH approximately 2.5, which corresponds to the 2,4-D pKa value. The amount of 2,4-D adsorbed was also found to depend on the NaCl concentration.     

Determination of n-alkanes and polycyclic aromatic hydrocarbons in atmospheric particulate and vapour phases in Oviedo, Spain, by GC-MS

A GC-MS procedure for the determination of hydrocarbons in air samples from Oviedo, Spain, was developed. Air hydrocarbons were sampled with a high volume sampler equipped with a holder containing a glass fiber filter, to trap the particulate phase, and two polyurethane foams to capture hydrocarbons of the vapour phase. Compounds were extracted with CH2Cl2 by Soxhlet extraction and then fractionated using column chromatography with alumina silica. Analyses of the fractions were performed by GC-MS in the electron ionization mode. PAHs and n-alkanes were the compounds examined in this work. Samples collected in the vicinity of the Faculty of Chemistry (a semi-urban area) were analysed. The total concentration of PAHs in the air samples analysed ranged from 28 to 76 ng m(-3). The total concentration of n-alkanes and PAHs in the vapour phase exceeded the concentration in the particulate phase in the samples analysed.     

A novel sensor for monitoring leakage of petroleum and other liquid hydrocarbons into soil environments

This paper describes the use of a potentially implantable infrared reflectometer for the qualitative detection of petroleum and a number of other hydrocarbon solvents. A rugged, low-power, re-useable sensor was evaluated in the laboratory for its ability to detect petrol in soil. A hydrophobic fluoropolymer was used as the sensing surface due to its high selectivity for petroleum hydrocarbons. The photocurrent reflected by this surface from a near IR source was measured to test for petroleum saturation within the membrane, which in turn was an indicator of petroleum in the surrounding soil. The simplicity in the sensor design enabled a stable, low cost detection method for petroleum and other hydrocarbons, ideal for use in sub-surface applications.