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.     

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.     

Excrement from Heron colonies for environmental assessment of toxic elements

Excrement cast from Great Blue Heron nests was collected during the nesting period of 1978 from four colonies in Washington and Idaho. Cheesecloth strips placed on the ground beneath the nests served as excrement collecting devices. Chemical analysis for lead, mercury and cadmium were performed on dried samples. Lead was the most abundant trace metal found in heron debris. The Idaho colony at Lake Chatcolet had an average concentration of 46 ppm in the beneath-nest samples and 6 ppm in control samples. A heron colony near Tacoma, Washington had beneath-nest samples averaging 28 ppm and control samples averaging 20 ppm. Two colonies located in the interior region of Washington had substantially lower concentrations of lead. The difference observed between colonies was attributed to their associations with a polluted watershed (Chatcolet colony) an interstate highway (Tacoma colony) and an unpopulated largely agricultural area (inland Washington).     

Field scale variability of cadmium and zinc in soil and barley

CaCl₂-extractable soil Cd and Zn contents have been suggested as a measure of bioavailability. To investigate the ability of this measure to reflect spatial patterns of Cd and Zn concentrations in barley (Hordeum vulgare L.) in an arable field, plant and soil samples were taken from a 0.5 ha area sandy soil contaminated with Cd and Zn. Cd and Zn contents in barley and yield were spatially variable. Yield was low, which may have been caused by Zn toxicity or atrazine turnover. For Cd, CaCl₂-extractable soil contents explained only 17% of the variation in Cd contents in grain, and for Zn no significant correlation was observed. Nevertheless, surface plots of CaCl₂-extractable soil contents and contents of barley grain illustrated their corresponding spatial patterns. Despite the poor linear correlation between CaCl₂-extractable soil-Cd and grain-Cd, a stochastic model for long term behaviour of Cd in field soils predicted observed variability in Cd contents of barley grain well from spatial variability of soil pH and organic matter content. The probabilistic model predicted behaviour of Cd in terms of probability, and was more appropriate than the deterministic approach.     

Persistent chlorinated pesticides in fish and cattle fat and their implications for human serum concentrations from the Sene-Gambian region

The concentrations of organochlorine pesticides (OCPs) in fish, shrimps, cattle fat and human serum samples from the Sene-Gambian region were measured using validated analytical methodologies. The results obtained were compared with those of other existing African studies and with data from other developing countries. In fish samples, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and HCB were detected with a frequency of 100%, whereas p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was detected in eight, heptachlorepoxide in six and endosulfansulfate in five of the nine fish samples. Relatively low concentrations of OCPs were found in cattle and shrimp fat samples. p,p'-DDE and alpha-hexachlorocyclohexane (alpha-HCH) were the most frequently identified. The sum of HCHs ranged from undetected to 13.3 ng g-1 fat, the sum of DDTs from 11.1 to 199.2 ng g-1 fat and the sum of endosulfans from not detected to 49.7 ng g-1 fat in fish and shrimps. In serum samples, alpha-HCH, p,p'-DDE, o,p'-DDT and p,p'-DDT were detected in all 16 pooled serum samples, whereas endosulfansulfate, methoxychlor, mirex, heptachlorepoxide and endrin were detected in 15 samples with most of the concentrations below 10 ng mL-1. The concentrations of OCPs in human serum were given on a serum lipid and whole serum volume basis. The implications for the human diet of these OCP concentrations in serum were investigated by means of biomagnification factors related to the log Kow values of the targeted compounds. The current use of HCH mixtures was suggested to explain the unusually high alpha-HCH concentration. The distribution pattern of these OCPs in humans was also discussed and compared with that in other studies.     

Fate and movement of atrazine, cyanazine, metolachlor and selected degradation products in water resources of the deep Loess Hills of Southwestern Iowa, USA

The environmental fate and movement of herbicides widely used for weed control in corn are assessed for a deep loess soil in southwestern Iowa. Beginning in the early 1980s, the herbicide-based weed control program emphasized the application of atrazine (ATR) or cyanazine (CYN) and metolachlor (MET) for both broadleaf and grass control. Between 1992 and 1995, concentrations of ATR, desethylatrazine (DEA), desisopropylatrazine (DIA), CYN and MET were measured in rainwater, both shallow and deep vadose zone water, and well water. Results show that the frequency of herbicide detections and the range and distribution of occurrences are dependent upon both landscape position and temporal inputs of recharge water from rainfall. Generally, DIA was observed more frequently and in higher mean concentration in well water than DEA, while DEA was observed more frequently than DIA in vadose zone groundwater. A chromatographic analogy is suggested to explain the occurrence patterns observed for both parent herbicide and degradation products within the unsaturated zone water. Analysis of rainwater samples collected during this time also revealed low concentrations of ATR, CYN and MET, with the timing of the detections indicative of non-local transport. Results show that the deep loess soil conducts both water and agricultural chemicals relatively rapidly and as such represents a production system which is vulnerable to contamination of shallow groundwater by herbicide-derived chemicals. Results also illustrate the importance of including major herbicide degradation products in water resource impact assessment studies.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

The interaction between physical and social-psychological factors in indoor environmental health

Indoor environmental health is now recognized as an important factor in preventing respiratory health problems in the United States. It is also a concern in Canada due to the amount of time that Canadians spend indoors because of cold weather and the potential for increased time indoors during the summer if theclimate warms. The negative health effects are often labeled assick building syndrome, but diagnosing a building or itsoccupants as sick is complicated by the variety of symptoms, thepresence of chronic versus acute symptoms and social andpsychological (socio-psychological) factors that may reduce theeffectiveness of an engineering solution. As a case study, thecontribution of various factors to indoor environmental health,in three buildings at the University of Toronto, was examinedusing five different methods. The results indicate that theinhabitants of the buildings consider features other than airquality in considering building health such as design,maintenance, funding cuts and socio-psychological factors.     

Using environmental stressor information to predict the ecological status of Maryland non-tidal streams as measured by biological indicators

In Maryland, U.S., an interim framework has recentlybeen developed for using biologically based thresholds, or `biocriteria', to assess the health of nontidal streams statewide at watershed scales. The evaluation of impairment is based on indices of biological integrity from the Maryland Biological Stream Survey (MBSS). We applied logistic regression to quantify how the biotic integrity of streams at a local scale is affected by cumulative effects resulting from catchment land uses, point sources, and nearby transmission line rights-of-way. Indicators for land use were developed from the remote sensing National Land Cover Data and applied at different scales. We determined that the risk of local impairment in nontidal streams rapidly increases with increased urban land use in the catchment area. The average likelihood of failing biocriteria doubled with every 10% points increment in urban land, thus an increase in urban land use from 0 to 20% quadruples the risk of impairment. For the basins evaluated in this study, catchments with more than 40–50% urban land use had greater than 80% probability of failing biocriteria, on average. Inclusion of rights-of-way and point sources in the model did not significantly improve the fit for this data set, most likely because of their low numbers. The overall results indicate that our predictive modeling approach can help pinpoint stream ecosystems experiencing or vulnerable to degradation.