Evaluating factors influencing groundwater vulnerability to nitrate pollution: developing the potential of GIS

The 1991 EU Nitrate Directive was designed to reduce water pollution from agriculturally derived nitrates. England and Wales implemented this Directive by controlling agricultural activities within their most vulnerable areas termed Nitrate Vulnerable Zones. These were designated by identifying drinking water catchments (surface and groundwater), at risk from nitrate pollution. However, this method contravened the Nitrate Directive because it only protected drinking water and not all waters. In this paper, a GIS was used to identify all areas of groundwater vulnerable to nitrate pollution. This was achieved by constructing a model containing data on four characteristics: the quality of the water leaving the root zone of a piece of land; soil information; presence of low permeability superficial (drift) material; and aquifer properties. These were combined in a GIS and the various combinations converted into a measure of vulnerability using expert knowledge. Several model variants were produced using different estimates of the quality of the water leaving the root zone and contrasting methods of weighting the input data. When the final models were assessed all produced similar spatial patterns and, when verified by comparison with trend data derived from monitored nitrate concentrations, all the models were statistically significant predictors of groundwater nitrate concentrations. The best predictive model contained a model of nitrate leaching but no land use information, implying that changes in land use will not affect designations based upon this model. The relationship between nitrate levels and borehole intake depths was investigated since there was concern that the observed contrasts in nitrate levels between vulnerability categories might be reflecting differences in borehole intake depths and not actual vulnerability. However, this was not found to be statistically important. Our preferred model provides the basis for developing a new set of groundwater Nitrate Vulnerable Zones that should help England and Wales to comply with the EU Nitrate Directive.     

Diuron occurrence and distribution in soil and surface and ground water associated with grass seed production

Little is known about the occurrence and distribution of the herbicide diuron [3-(3,4-dichlorophenyl)-1,1-dimethyl urea] in soil, ground water, and surface water in areas affected by grass-seed production. A field study was designed to investigate the occurrence and distribution of diuron and its transformation products at a poorly drained field site located along an intermittent tributary of Lake Creek in the southern Willamette Valley of Oregon. The experimental sites consisted of a field under commercial grass seed production with a cultivated riparian zone and a second site that was part of the same grass seed field but with a noncultivated riparian zone. Diuron and its transformation product DCPMU [3-(3,4-dichlorophenyl)-1-methylurea] were the only significant residues detected in this study. Concentrations of diuron in surface water declined from a maximum of 28 microg/L immediately following application to low levels that persisted as long as flow was present. Diuron and DCPMU concentrations in shallow ground water (15-36 cm below ground surface) were highest (2-13 microg/L) in the zone immediately adjacent (0.5 m) to Lake Creek and indicated the influence of stream water on shallow ground water near the stream. Diuron and DCPMU detected in soil prior to the second season's application indicated the persistence of diuron and DCPMU from the previous year's application. Surface runoff during the rainy season removes only a very small percentage (<1%) of the applied herbicide. In addition, no evidence was obtained for the downward transport of diuron or its transformation products to deep ground water.     

In situ treatment of metals in contaminated soils with phytate

Batch experiments were conducted to evaluate the ability of various forms of phytate, the hexaphosphoric form of myo-inositol (IP6), to immobilize U, Ni, and other inorganic contaminants in soils and sediments. A Ca-phytate precipitate (Ca(n)-IP6), dodeca sodium-phytate (Na12-IP6), and hydroxyapatite (HA) were added to contaminated soil at rates of 0, 10, 25, and 50 g kg(-1) and equilibrated in 0.001 M CaCl2. The samples were then centrifuged, the solution pH was measured, and the supernatants were filtered prior to analysis for dissolved organic carbon (DOC), U, Ni, P, and other inorganic contaminants, such as As, Cr, Se, and Pb. The residual sediments were air-dried prior to characterization by analytical electron microscopy and extraction with the Toxicity Characteristic Leaching Procedure (TCLP). The solubility of several metals (e.g., U, Pb, Cu) increased with increasing Na12-IP6 when compared with the nonamended control. In some cases immobilization was observed at the lowest Na12-IP6 application rate (10 g kg(-1)) with an increase in solubility observed at the higher rates, demonstrating the importance of metal to ligand ratio. In contrast, Ca(n)-IP6 and HA decreased the solubility of U, Ni, Al, Pb, Ba, Co, Mn, and Zn. For example, soluble U decreased from 2242 to 76 microg kg(-1) and Ni from 58 to 9.6 mg kg with the Ca(n)-IP6 addition, similar to the results observed for HA. Arsenic and Se solubility increased for HA and both forms of IP6, but to a much greater degree for Na12-IP6, suggesting that the increase in pH observed for HA and Na12-IP6, combined with added competition from PO4 and IP6 for sorption sites, resulted in the release of sorbed oxyanion contaminants. The analytical electron microscopy results indicated that metals such as U and Ni were closely associated with secondary Al-rich precipitates in the HA-treated soils, rather than unreacted HA. The analytical electron microscopy results were less definitive for the Ca(n)-IP6-treated soil, although the residual P-containing material was enriched in Al, with lesser amounts of U and Ni.     

Nitrogen removal and nitrate leaching for two perennial,sod-based forage systems receiving dairy effluent

In northern Florida, year-round forage systems are used in dairy effluent sprayfields to reduce nitrate leaching. Our purpose was to quantify forage N removal and monitor nitrate N (NO3(-)-N) concentration below the rooting zone for two perennial, sod-based, triple-cropping systems over four 12-mo cycles (1996-2000). The soil is an excessively drained Kershaw sand (thermic, uncoated Typic Quartzip-samment). Effluent N rates were 500, 690, and 910 kg ha(-1) per cycle. Differences in N removal between a corn (Zea mays L.)-bermudagrass (Cynodon spp.)-rye (Secale cereale L.) system (CBR) and corn-perennial peanut (Arachis glabrata Benth.)-rye system (CPR) were primarily related to the performance of the perennial forages. Nitrogen removal of corn (125-170 kg ha(-1)) and rye (62-90 kg ha(-1)) was relatively stable between systems and among cycles. The greatest N removal was measured for CBR in the first cycle (408 kg ha(-1)), with the bermudagrass removing an average of 191 kg N ha(-1). In later cycles, N removal for bermudagrass declined because dry matter (DM) yield declined. Yield and N removal of perennial peanut increased over the four cycles. Nitrate N concentrations below the rooting zone were lower for CBR than CPR in the first two cycles, but differences were inconsistent in the latter two. The CBR system maintained low NO3(-)-N leaching in the first cycle when the bermudagrass was the most productive; however, it was not a sustainable system for long-term prevention of NO3(-)-N leaching due to declining bermudagrass yield in subsequent cycles. For CPR, effluent N rates > or = 500 kg ha(-1) yr(-1) have the potential to negatively affect ground water quality.     

Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Cadmium,chromium and lead contamination of Athene noctua,the little owl,of Bologna and Parma,Italy

A study was conducted to determine cadmium, chromium and lead concentrations in liver and brain of 52 little owls (Athene noctua) from two provinces of Emilia Romagna region, with the aim of furnishing indirect information concerning contamination of their habitat, also considering possible environmental dispersion of the metals. Metal analysis was performed by atomic absorption spectrophotometry with graphite furnace. Variance analysis with sampling area, gender and age shows that no statistical difference was found for gender, while a significant difference (P<0.05) was found for cadmium and lead, but not for chromium, when sampling areas and age were of concern. For all metals highest mean concentrations were found in liver (170 ppb for cadmium, 297 ppb for chromium and 312 ppb for lead). These levels can be considered as indicative of chronic exposure to low and "background" amounts of pollutants and they are of no toxicological concern, as they are always well below the toxic thresholds defined for each metal. The present study can be considered as a starting point for further analyses, aimed to the definition of any possible subtle effect (e.g. effects on enzymes activity) and of any possible correlation between levels of pollutants and appearance of possible adverse effects. It also furnished useful data for diagnostic cases and potentially for monitoring local contamination.     

Do vesicle cells of the red alga Asparagopsis (Falkenbergia stage) play a role in bromocarbon production?

The Rhodophyceae (red algae) are an established source of volatile halocarbons in the marine environment. Some species in the Bonnemaisoniaceae have been reported to contain large amounts of halogens in structures referred to as vesicle cells, suggesting involvement of these specialised cells in the production of halocarbons. We have investigated the role of vesicle cells in the accumulation and metabolism of bromide in an isolate of the red macroalga Asparagopsis (Falkenbergia stage), a species known to release bromocarbons. Studies of laboratory-cultivated alga, using light microscopy, revealed a requirement of bromide for both the maintenance and formation of vesicle cells. Incubation of the alga in culture media with bromide concentrations below 64 mgl(-1) (the concentration of Br(-) in seawater) resulted in a decrease in the proportion of vesicle cells to pericentral cells. The abundance of vesicle cells was correlated with bromide concentration below this level. Induction of vesicle cell formation in cultures of Falkenbergia occurred at concentrations as low as 8 mgl(-1), with the abundance of vesicle cells increasing with bromide concentration up to around 100 mgl(-1). Further studies revealed a positive correlation between the abundance of vesicle cells and dibromomethane and bromoform production. Interestingly, however, whilst dibromomethane production was stimulated by the presence of bromide in the culture media, bromoform release remained unaffected suggesting that the two compounds are formed by different mechanisms.     

The interactions between plant growth,vegetation structure and soil processes in semi-natural acidic and calcareous grasslands receiving long-term inputs of simulated pollutant nitrogen deposition

Regular applications of ammonium nitrate (35-140 kg N ha(-1) year(-1)) and ammonium sulphate (140 kg N ha(-1) year(-1)) to areas of acidic and calcareous grassland in the Derbyshire Peak District over a period of 6 years, have resulted in significant losses in both overall plant cover, and the abundance of individual species, associated with clear and dose-related increases in shoot nitrogen content. No overall growth response to nitrogen treatment was seen at any stage in the experiment. Phosphorus additions to the calcareous plots did however lead to significant increases in plant cover and total biomass, indicative of phosphorus limitation in this system. Clear and dose-related increases in soil nitrogen mineralization rates were also obtained, consistent with marked effects of the nitrogen additions on soil processes. High nitrification rates were seen on the calcareous plots, and this process was associated with significant acidification of the 140 kg N ha(-1) year(-1) treatments.     

Influence of temperature and time on phosphorus removal in swine manure during batch aeration

This study was conducted to investigate the effects of temperature and time on the mechanisms of phosphorus removal in swine manure during aeration. Removal of soluble orthophosphates significantly increased with aeration time and temperature. Successive significant ortho-P removals were observed between days one and nine but no significant additional removals were recorded thereafter. Removals were significantly higher at temperatures of 20 and 25 degrees C than at temperatures of 5, 10, and 15 degrees C and ranged between 22.9 to 31.0%. Insoluble inorganic phosphorus also changed significantly with aeration time and temperature and with a similar trend as soluble orthophosphates. The pH of the manure explained 92 and 87% of the content of insoluble inorganic phosphorus at lower temperatures (5, 10, 15 degrees C) and at higher temperatures (20, and 25 degrees C), respectively. Organic phosphorus and aerobes growth patterns were similar to that of soluble orthophosphates removal. The rapid growth of aerobes was most probably the principal factor behind a rapid soluble ortho-P removal above 15 degrees C. The contribution of inorganic phosphates to the removal of soluble orthophosphates was approximately 61% while that due to organic P was approximately 35%. Precipitation was found to be the principal mechanism governing removal of soluble ortho-P in swine manure during aeration treatments.     

Detecting the signal of atmospheric N deposition in recent national-scale vegetation change across Britain

Model estimates of NO_y and NH_x deposition across Britain for 1996 (5 km square resolution) were applied as explanatory variables to account for national-scale, fine-grained changes in plant species composition between 1990 and 1998. Plant species data were recorded from up to 27 fixed plots located within a stratified random sample of 596 1 km². The response variable was a cover-weighted Ellenberg fertility score for each plot. Analyses were carried out separately for woodlands, semi-natural grasslands and heaths/bogs. Most of the variation in the botanical response variable occurred between plots within squares and so could not be explained by the model deposition data. NH_x deposition estimates accounted for significant, but small components of between 1 km² variation in the change in Ellenberg score in grasslands (5.6%) and heath/bogs (9.8%) but not woodlands. NO_y deposition estimates were not significantly associated with vegetation change. Linear models provided the best fit and the slope of the relationship was lower for heath/bogs than grasslands. Further signal attribution at sub-kilometre square scales requires the development of fine-grained models of N deposition that can be generalised across regional sampling domains.