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.     

Performance evaluation of a sorbent tube sampling method using short path thermal desorption for volatile organic compounds

Air sampling, using sorbents, thermal desorption and gas chromatography, is a versatile method for identifying and quantifying trace levels of volatile organic compounds (VOCs). Thermal desorption can provide high sensitivity, appropropriate choices of sorbents and method parameters can accommodate a wide range of compounds and high humidity, and automated short-path systems can minimize artifacts, losses and carry-over effects. This study evaluates the performance of a short-path thermal desorption method for 77 VOCs using laboratory and field tests and a dual sorbent system (Tenax GR, Carbosieve SIII). Laboratory tests showed that the method requirements for ambient air sampling were easily achieved for most compounds, e.g., using the average and standard deviation across target compounds, blank emissions were < or = 0.3 ng per sorbent tube for all target compounds except benzene, toluene and phenol; the method detection limit was 0.05 +/- 0.08 ppb, reproducibility was 12 +/- 6%, linearity, as the relative standard deviation of relative response factors, was 16 +/- 9%, desorption efficiency was 99 +/- 28%, samples stored for 1-6 weeks had recoveries of 87 +/- 9%, and high humidity samples had recoveries of 102 +/- 12%. Due to sorbent, column and detector characteristics, performance was somewhat poorer for phenol groups, ketones, and nitrogen containing compounds. The laboratory results were confirmed in an analysis of replicate samples collected in two field studies that sampled ambient air along roadways and indoor air in a large office building. Replicates collected under field conditions demonstrated good agreement except for very low concentrations or large (> 41 volume) samples of high humidity air. Overall, the method provides excellent performance and satisfactory throughput for many applications.     

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.     

Assessing land use impacts on flood processes in complex terrain by using GIS and modeling approach

A distributed hydrologic modeling and GIS approach is applied for the assessment of land use impact in the Steinsel sub-basin, Alzette, Grand-Duchy of Luxembourg. The assessment focuses on the runoff contributions from different land use classes and the potential impact of land use changes on runoff generation. The results show that the direct runoff from urban areas is dominant for a flood event compared with runoff from other land use areas in this catchment, and tends to increase for small floods and for the dry season floods, whereas the interflow from forested, pasture and agricultural field areas contributes to the recession flow. Significant variations in flood volume, peak discharge, time to the peak, etc., are found from the model simulation based on the three hypothetical land use change scenarios.