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).     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Soil properties and crop productivity as influenced by flyash incorporation in soil

Field experiments were carried out during 1996–97at Gulawathi, Muthiani and Salarpur Villages, IARI Farm, NewDelhi and NCPP Campus, Dadri to evaluate changes in soilcharacteristics and growth of wheat (Triticum aestivum L.),mustard (Brassica juncea L.), lentil (Lence esculentaMoench.), rice (Oryza sativa L.) and maize (Zea mays L.) byvarying amounts of flyash addition (up to 50t ha^-1) in soils atsowing/transplanting time of crops. Flyash addition in areasadjoining NCPP Thermal Power Plant, Dadri, Ghaziabad, U.P.ranged from 5–12 t ha^-1 yr^-1 in 1995–96. Shoot and root growthand yield of test crops at different locations after flyashincorporation resulted in beneficial effects of flyashaddition in most cases. The silt dominant texture of flyashimproved loamy sand to sandy loam textures of the surfacesoils at the farmers' fields. The increased growth in yield ofcrops with flyash incorporation was possibly due tomodifications in soil moisture retention and transmissioncharacteristics, bulk density, physico-chemical characterssuch as pH and EC and organic carbon content. The response offlyash addition in the soil on soil health and cropproductivity needs to be evaluated on long-term sustainableaspects.     

Using Multiple Antibiotic Resistance and land use characteristics to determine sources of fecal coliform bacterial pollution

Multiple Antibiotic Resistance (MAR) analysis and regression modeling techniques were used to identify surface water areas impacted by fecal pollution from human sources, and to determine the effects of land use on fecal pollution in Murrells Inlet, a small, urbanized, high-salinity estuary located between Myrtle Beach and Georgetown, South Carolina. MAR analysis was performed to identify areas in the estuary that are impacted by human-source fecal pollution. Additionally, regression analysis was performed to determine if an association exists between land use and fecal coliform densities over the ten-year period from 1989 to 1998. Land-use variables were derived using Geographic Information System (GIS) techniques and were used in the regression analysis.MAR analyses were conducted by comparing the frequency and patterns of antibiotic resistance found in Escherichia coli isolates derived from surface water samples and from sewage sources in the Murrells Inlet sewage collection system. The MAR results suggest that the majority of the fecal pollution detected in the Murrells Inlet estuary may be from non-human sources, including fecal coliforms isolated from areas in close proximity to high densities of active septic tanks.A MAR Index, which measures the frequency of antibiotic resistance, was calculated for each of twenty-three water samples and nine sewage samples. The antibiotic resistance pattern comparisons were performed using cluster analysis. Although the MAR indices indicated that several surface water sites had potential human-source contamination, the cluster analysis suggests that only one sampling site had MAR patterns that were similar to those found in the sewage samples. This site was in close proximity to several large pleasure boats as well as a sewage collection system lift station, but was not near areas with active septic tanks. The results of the regression analysis also suggest that sewage sources and rainfall runoff from urbanized areas may contribute to fecal pollution in the estuary.     

A Survey of Trace Metals in Vegetation, Soil and Lower Animal Along Some Selected Major Roads in Metropolitan City of Lagos

The concentration of trace metals (Cd, Cu, Pb and Zn) in a total of 144 samples of grass, soil and lower animal (earthworm, Lybrodrilus violaceous) were collected and analysed for their metallic content. Levels of cadmium ranged from 0.01–0.07 g g^–1; 0.01–0.12 g g^–1 and from trace–0.05 g g^–1 dry weight for plant, soil and animal samples respectively. Mean concentration of copper ranged 0.10–1.48 g g^–1; 0.10–2.90 g g^–1 and 0.01–0.08 g g^–1 for samples in similar order as above. The levels of Pb varied from 0.01–0.14 g g^–1; 0.02–0.23 g g^–1 and from trace–0.07 g g^–1 while that of Zn ranged from 0.19–1.80 g g^–1; 0.51–3.35 g g^–1and 0.01–0.08 g g^–1 also in the same order of samples as mentioned above. Levels of metals in soil samples were higher than the background levels with the exception of Zn but lower than European Union (EU) limits. The results generally revealed the presence of metals in plant and animal samples and metal dynamics up the food chain is highly possible. Acceptable recoveries of the spiking experiment validate the experimental protocol.     

SPATIAL ANALYSIS AND EUTROPHICATION ASSESSMENT FOR CHLOROPHYLL a IN TAIHU LAKE

Spatial structure analysis and kriging analysis have been identified to be useful tools in illustrating the spatial patterns of variables. Taihu Lake is one of the largest fresh water lakes in China, and has suffered serious eutrophication in recent years due to the rapid economic development and growing environmental pollution in the Taihu Catchment. In this paper, spatial structural analysis, kriging interpolation and eutrophication assessment were carried out for chlorophyll a in the lake. Studies show that spherical model could be applied to fit all experimental variograms. Positive nuggets were observed for three directions except NE–SW direction. The variograms show some anisotropy with anisotropic ratio falling within 1.76. The spatial structural patterns of chlorophyll a in the lake were affected by factors such as distribution of pollution sources, water flow and wind. Two-dimensional ordinary block kriging was applied for interpolation process. An eutrophication assessment map was also made based on a water-quality evaluation standard. Results show that the content of chlorophyll a in Taihu Lake was quite high. The whole lake has suffered serious eutrophication. However, the eutrophic situation varied in space. Higher contents of chlorophyll a appeared mainly in the northern part of the lake.     

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.     

Arsenic compounds in the haemolymph of the Dungeness crab, Cancer magister, as determined by using HPLC on-line with inductively coupled plasma mass spectrometry

Arsenobetaine, two arsenosugars, dimethylarsinate and several unidentified arsenic species were detected in extracts of the haemolymph of the Dungeness crab, Cancer magister, by using HPLC-ICP-MS. This is the first report of the presence of arsenosugars in the haemolymph/blood of marine animals. Total, extractable and residual arsenic concentrations were determined by ICP-MS. The concentration of total arsenic was in the range of 1.4-3.8 [micro sign]g ml(-1). Nearly all (98%) the arsenic was found to be extractable, and accounted for primarily by arsenobetaine, two arsenosugars and dimethylarsinate. The results demonstrate that arsenic compounds present in the diet of crabs are not fully metabolized in the gut. They are, at least partly, taken up into the haemolymph. The concurrence of arsenobetaine and arsenosugars suggests that the use of repeated haemolymph sampling in crustaceans could facilitate investigations into the kinetics of the biotransformation pathways of arsenic compounds. Finally, the present study clearly demonstrates the unique capabilities of HPLC-ICP-MS for the detection and identification of minor arsenic components amongst the predominant arsenobetaine.     

Numerical Analyses of Soft Bottom Macroinvertebrates to Diagnose the Pollution in Tropical Coastal Waters

Soft bottom benthic organisms especially polychaetes are known to adapt as r or k selected strategies to different gradients of pollution. This will result in changes of benthic community structure from that of normal structure. There are a number of techniques to assess the impact of pollution on benthic community structure. Hence, to test this hypotheses some of the univariate and multivariate techniques were applied to soft bottom macro-invertebrates data of coastal waters of Mangalore, central west coast of India, a hot-spot area. Univariate techniques such as Pearson Rosenberg Model (PRM), abundance biomass comparison curve (ABC), geometrical class distribution, dominance-diversity curve, benthic community structure indices and multivariate techniques such as cluster classification, multidimensional scaling (MDS) and principal component analysis (PCA) were used to discriminate and diagnose the disturbance among the sites. Effectiveness and applicability of some of the above techniques are highlighted and discussed with the present set of data for environmental impact assessment studies.