Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPA's Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.     

Young northern pike,yellow perch and crayfish as bioindicators in a mercury contaminated watercourse

Young-of-the-year and yearling northern pike (Esox lucius), yearling yellow perch (Perca flavescens) and adult crayfish (Orconectes virilis) were collected in the mercury-contaminated Wabigoon/English/Winnipeg River System, Ontario, and analyzed for total mercury. Analysis of mercury concentrations in these organisms produced consistent geographical trends; i.e. mercury concentrations in biota downstream of Dryden > English River system > Winnipeg River system > control sites. In the Wabigoon River system the bioavailability of mercury increases with distance downstream of the historical point source. Mercury concentrations in the biota studied were highly correlated with mercury concentrations in fish species which are of sport and commercial interest. The locations where young fish obtain their bodyburdens are known typically within 100 m. The biota studied compare favourably with the criteria proposed by Phillips (1980) as prerequisites for biological indicators. The wide distribution of young pike, perch and crayfish in North America, Europe and Asia may enhance their appeal as biomonitors.The views expressed are those of the authors and do not necessarily reflect the views of the Ontario Ministry of the Environment. No endorsement should be inferred.     

Temporal variation in a coral reef community at Pattaya Bay,Gulf of Thailand

Changes in the fringing coral reef community of a small island (Ko Nok) at Pattaya Bay, Gulf of Thailand, were examined at the beginning and at the end of a 3-year period using 7m×7m permanent quadrats for benthic organisms, and visual census along 100m transects for fish. The coral community was dominated by Porites lutea in terms of colony number and areal cover throughout the period. Variations in the community structure parameters on opposite sides of the island indicated increasing dissimilarity with time. Little variation in live coral cover was noted, but colony number and species diversity declined on both sides. The abundance of edible fish species dropped while that of non-edible species increased over the 3-year period, indicating selective removal of the former category through fishing. Impacts from both human and natural influences are implicated in these changes.     

Analysis of two-way layout of count data with negative binomial variation

A number of methods has been proposed for dealing with single-factor or factorial experiments when the requirements for performing the normal theory analysis of variance procedure are not satisfied. This paper suggests the use of the likelihood ratio statistic for testing the main effects and the interaction between the factors in two-way layout of count data following negative binomial distributions with a common dispersion parameter. The likelihood ratio statistic for testing the equality of the dispersion parameters of several groups of count data is also derived. The methods is illustrated by an example concerning the study of spatial and temporal variation of bacterial counts.     

Spatial analysis and mapping the annual mean concentrations of acidity and major ions in precipitation over the United Kingdom in 1986

The composition of precipitation is being monitored in collectors sited throughout the United Kingdom. In the first year, 1986, hydrogen ion, nitrate, ammonium and non-marine sulphate were measured in samples from 47 sites and annual mean concentrations determined. Spatial analysis based on Regionalized Variable Theory revealed autocorrelation in all four ions and reasonable bounded models were fitted to the sample variogram of all four. These were then used to estimate values of a fine mesh grid by simple kriging, and the estimates were then contoured. The estimation errors were similarly mapped, and both sets of maps are presented. The maps show that concentrations of these ions are greatest in eastern parts of the country, as expected from consideration of European emissions and weather patterns. For the first time estimation errors were also mapped and show how the network could be improved.     

Atmospheric haze: Its sources and effects on visibility in rural areas of the continental United States

Spatial and temporal trends in visibility are examined at a national level. It is shown that visibility is impaired in all antional parks approximately 90% of the time, and that eastern visibilities are about 10 times lower than western visibilities. Measurement of atmospheric particulates that affect visibility shows that sulfates associated with man-made emissions of sulfur dioxide are the single largest contributor to visibility reduction, except in the northwestern United States, where organic aerosols contribute significantly. In the East, coal fired power plants along the Ohio River Vallery contribute the most SO₂, while oil refining activities and other industrial sources in southern California, copper smelters in southern Arizona, and industrial activity along the Gulf Coast of Mexico contribute most of the SO₂, and thus sulfates, in the West.Contribution from Fourth World Wilderness Congress-Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.The assumptions, findings, conclusions, judgments and views presented herein are those of the authors and should not be interpreted as necessarily representing official National Park Service policies.     

Organochlorine contaminants in seabird eggs from the Pacific coast of Canada, 1971–1986

Eggs were collected from seven seabird species at colonies on the British Columbia coast from 1983 to 1986 and analyzed for organochlorine contaminants. Total PCB levels (wet weight) were highest in double-crested cormorants (Phalacrocorax auritus) from the Fraser estuary (2.91 mg kg^-1) and the Strait of Georgia (3.79 mg kg^-1). Highest DDE levels were in fork-tailed storm-petrels (Oceanodroma furcata) from the Queen Charlotte Islands (1.68 mg kg^-1). Organochlorine levels were generally lower in eggs from the mid 1980s than in those collected in the early 1970s. Organochlorine levels in Pacific alcids and hydrobatids foraging in offshore locations were compared to those in the same or ecologically similar species from the Canadian Atlantic coast. DDT- and HCH-related compounds were higher in Pacific populations while levels of dieldrin, oxychlordane, and HCB were generally lower. With the exception of -HCH, levels of all measured organochlorines were lower in cormorants breeding in the Fraser River estuary than in cormorants from the St. Lawrence River estuary on the Atlantic coast.     

Robust graphical methods for diagnosing trend in irregularly spaced water quality time series

Graphical methods can play an important role in the reliable assessment of trends in typically ill behaved river quality data series both as diagnostic tools and as visual corroborative evidence when assumptions required for formal statistical tests are not met. Robust, graphically-oriented trend diagnosis procedures are presented for data series characterized by nonnormal populations, uneven time spacing, nonmonotonic trend and other factors which can create serious problems for standard parametric time series methods. Cleveland's robust locally weighted regression (RLWR) developed for investigating nonlinearity in x-y scatterplots is adapted as a robust/resistant smoothing filter for the analysis of irregular time series comprising quantitative observations. Low powered RLWR trend lines reveal temporally local phenomena, e.g. abrupt jumps (often associated with point source impacts) and periodicities, while higher powered RLWR yields smooth lines characterizing medium and longer term trends. Simple variants of Tukey smoothing concepts are developed for series with censored observations. Applications to Ontario river quality series reveal that graphical evidence is frequently sufficient to obviate the need for formal trend testing. The methods are generally applicable to most time series.