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.     

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).     

A study of the distribution of lead, cadmium and copper between water and kaolin, bentonite and a river sediment

Experiments were carried out to monitor the equilibrium distribution of lead, cadmium and copper between an aqueous phase modelling natural water and a solid phase modelling natural sediment, under varying conditions. The aqueous phase was analysed using ETAAS and differential pulse anodic stripping voltammetry (DPASV), whereas XRD and FTIR were used to study the solid phase. Sorption isotherms at constant pH were measured. Conditional distribution constants were calculated as functions of the pH, the time of equilibration and the amount of solid material. The results obtained stress the need for standardization of the approaches to the study of water-sediment interactions in order to be able to evaluate and compare the extensive data from field measurements and to predict these interactions.     

Insecticide Contamination of Jamaican Environment. V. Island-Wide Rapid Survey of Residues in Surface and Ground Water

Residues of organochlorines and organophosphates were determined by gas chromatography in water and sediment from 26 locations in 17 major rivers, 7 natural springs and 13 wells across Jamaica. Samples were collected on only one occasion between May and July, 1994. Residues of endosulfan were detected in all but three rivers; -endosulfan in 15 samples of sediment (0.9–108.1, mean = 28.93, S.E. = 7.198 g kg-1) and 13 of water (0.01–0.35, mean = 0.11, S.E. = 0.035 g L-1), -endosulfan in 5 sediment (15.29–49.35, mean = 30.56, S.E. = 7.132 g kg-1) and 12 water (0.05–0.31, mean = 0.14, S.E. = 0.031 g L-1) samples, and endosulfan sulphate in waters of three rivers (0.003–0.244 g L-1). Chlorpyrifos was present in 9 sediment (0.423-135.2, mean = 18.38, S.E. = 10.699 g kg-1) and two water (0.001–0.022 g L-1) samples, diazinon and ethoprophos in the sediment of one river each. Mean levels (g L-1) of and isomers and sulphate of endosulfan were 0.16 (S.E. = 0.057), 0.12 (S.E. = 0.036) and 0.15 (S.E. = 0.089), respectively, in four of the seven springs and 0.23 (S.E. = 0.052), 0.11 (S.E. = 0.029) and 0.26 (S.E. = 0.088), respectively, in seven of the thirteen wells monitored.     

A catalogue of urban hydrocarbons for the city of Leeds: atmospheric monitoring of volatile organic compounds by thermal desorption-gas chromatography

A method has been developed for the speciation and quantitative determination of hydrocarbons in urban air in the city of Leeds. Hydrocarbons were pre-concentrated by adsorbent tube air sampling and analyzed using thermal desorption and gas chromatography with flame ionization detection and structural confirmation by mass spectrometric detection. While automated volatile organic compound (VOC) analyzers produced data for a maximum of about 30 compounds simultaneously, with the method described here, a total of 68 C6-C12 hydrocarbons were measured simultaneously in one analysis at parts per billion (ppb) levels. Several monitoring surveys were performed, one during the winter of 1993 and the other in the summer of 1994, at a number of sites to investigate the levels of VOCs identified in the urban air of Leeds.     

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.     

Atrazine and Alachlor Inputs to Surface and Ground Waters in Irrigated Corn Cultivation Areas of Castilla-Leon Region, Spain

The inputs of atrazine and alachlor herbicides to surface and ground waters from irrigated areas dedicated to corn cultivation in the Castilla-León (C-L) region (Spain) as related to the application of both herbicides were studied. Enzyme-linked immunosorbent assays (ELISA) were used for monitoring the atrazine and alachlor concentrations in 98 water samples taken from these areas. Seventy-nine of the samples were of ground waters and 19 were of surface waters. The concentration ranges of the herbicides detected in the study period (October 1997–October 1998) were 0.04–25.3 g L^–1 in the surface waters and 0.04–3.45 g L^–1 in the ground waters for atrazine, and 0.06–31.9 g L^–1 in the surface waters and 0.05–4.85 g L^–1 in the ground waters in the case of alachlor. The highly significant correlation observed between the concentrations of both herbicides in the surface waters (r = 0.89, p < 0.001) pointed to a parallel transport of atrazine and alachlor to these waters. A study was made of the temporal evolution of the concentrations of both herbicides, and it was found a maximum recharge of atrazine in the ground waters for April 1998 and of alachlor in October 1997 and October 1998. The temporal evolution of the concentrations of both herbicides in surface waters was parallel. The highly significant correlations observed between atrazine concentrations determined by ELISA and by HPLC (r = 0.92, p < 0.001) and between alachlor concentrations also determined by both methods (r = 0.96, p < 0.001) confirmed the usefulness of ELISA for monitoring both herbicides in an elevated number of samples. Using HPLC, the presence in some waters of the alachlor ethanesulfonate (ESA) metabolite was found at a concentration range of 0.52–4.01 g L^–1. However the interference of ESA in the determination of alachlor by ELISA was negligible. The inputs of atrazine and alachlor to waters found in this study, especially the inputs to ground waters, could pose a risk for human health considering that some waters, though sporadically, are even used for human consumption.     

IMPACTS OF VISITORS ON SOIL AND VEGETATION OF THE RECREATIONAL AREA “NACIMIENTO DEL RÍO MUNDO” (CASTILLA-LA MANCHA, SPAIN)

This study examines the effects of recreational use on the soil and vegetation at a site of ecological importance (Nacimiento del Río Mundo, Albacete, Spain). The most visited sites showed increased soil compaction of approximately 50%, bare ground increase to 61 ± 10% and a decrease in richness (from 25 ± 2 to 15 ± 2 species), diversity (from 4.0 ± 0.1 to 2.7 ± 0.4) and stratification of plant species (from 80 ± 11 to 21 ± 4%). The most visited sites had 90% less plant species as compared to the least visited. Intense use was associated with the presence of nitrophilous plant and vegetal species with a morphology adapted to heavy trampling. The recreational areas showed a distribution pattern of impact radiating outwards from the most used and degraded point. At the most visited point, Los Chorros (the spring of the river), the impact radiated outwards for about 20 m. A pilot experiment examining the effects of one-year restriction to visitors for access to a formerly impacted area showed a plant cover increase by anthropic and not by native species of 57 percent units.     

24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).