Owen Fenton

Factors affecting nitrate distribution in shallow groundwater under a beef farm in South Eastern Ireland

Groundwater contamination was characterised using a methodology which combines shallow groundwater geochemistry data from 17 piezometers over a 2 yr period in a statistical framework and hydrogeological techniques. Nitrate-N (NO3-N) contaminant mass flux was calculated across three control planes (rows of piezometers) in six isolated plots. Results showed natural attenuation occurs on site although the method does not directly differentiate between dilution and denitrification. It was further investigated whether NO3-N concentration in shallow groundwater (<5 m below ground level) generated from an agricultural point source on a 4.2 ha site on a beef farm in SE Ireland could be predicted from saturated hydraulic conductivity (Ksat) measurements, ground elevation (m Above Ordnance Datum), elevation of groundwater sampling (screen opening interval) (m AOD) and distance from a dirty water point pollution source. Tobit regression, using a background concentration threshold of 2.6 mg NO3-N L(-1) showed, when assessed individually in a step wise procedure, Ksat was significantly related to groundwater NO3-N concentration. Distance of the point dirty water pollution source becomes significant when included with Ksat in the model. The model relationships show areas with higher Ksat values have less time for denitrification to occur, whereas lower Ksat values allow denitrification to occur. Areas with higher permeability transport greater NO3-N fluxes to ground and surface waters. When the distribution of Cl- was examined by the model, Ksat and ground elevation had the most explanatory power but Ksat was not significant pointing to dilution having an effect. Areas with low NO3 concentration and unaffected Cl- concentration points to denitrification, low NO3 concentration and low Cl- chloride concentration points to dilution and combining these findings allows areas of denitrification and dilution to be inferred. The effect of denitrification is further supported as mean groundwater NO3-N was significantly (P<0.05) related to groundwater N2/Ar ratio, redox potential (Eh), dissolved O2 and N2 and was close to being significant with N2O (P=0.08). Calculating contaminant mass flux across more than one control plane is a useful tool to monitor natural attenuation. This tool allows the identification of hot spot areas where intervention other than natural attenuation may be needed to protect receptors.

Determining Phosphorus and Sediment Release Rates from Five Irish Tillage Soils

The aim of this study was to compare the nutrient and sediment releases from five Irish tillage soils, inclined at 10- and 15-degree slopes, under a simulated rainfall intensity of 30 mm h(-1) in a controlled laboratory study. Using the relationship between soil test phosphorus (STP) in the five soils and the dissolved reactive phosphorus (DRP) released in surface runoff, a runoff dissolved phosphorus risk indicator (RDPRI) was developed to identify the STP level for Irish tillage soils above which there may be a potential threat to surface water quality. The results of this study indicated that tillage soils may produce surface runoff P concentrations in excess of 30 microg L(-1) (the value above which eutrophication of rivers is likely to occur and the maximum allowable concentration of DRP in rivers under the EU Water Framework Directive, WFD) if their Morgans phosphorus (P(m)), Mehlich 3 phosphorus (M3-P), and water extractable phosphorus (WEP) concentrations exceed 9.5 mg L(-1), 67.2 mg kg(-1), and 4.4 mg kg(-1), respectively. This work reinforces the statutory agronomic based requirements of the European Communities (Good Agricultural Practice for Protection of Waters) Regulations 2009 (S.I. no. 101 of 2009). A statistical analysis showed that WEP gave the best prediction for runoff DRP.

Denitrification and indirect N2O emissions in groundwater: Hydrologic and biogeochemical influences

Identification of specific landscape areas with high and low groundwater denitrification potential is critical for improved management of agricultural nitrogen (N) export to ground and surface waters and indirect nitrous oxide (N₂O) emissions. Denitrification products together with concurrent hydrogeochemical properties were analysed over two years at three depths at two low (L) and two high (H) permeability agricultural sites in Ireland. Mean N₂O-N at H sites were significantly higher than L sites, and decreased with depth. Conversely, excess N₂-N were significantly higher at L sites than H sites and did not vary with depth. Denitrification was a significant pathway of nitrate (NO₃⁻-N) reduction at L sites but not at H sites, reducing 46-77% and 4-8% of delivered N with resulting mean NO₃⁻-N concentrations of 1-4 and 12-15 mg N L⁻¹ at L and H sites, respectively. Mean N₂O-N emission factors (EF₅g) were higher than the most recent Intergovernmental Panel on Climate Change (IPCC, 2006) default value and more similar to the older IPCC (1997) values. Recharge during winter increased N₂O but decreased excess dinitrogen (excess N₂-N) at both sites, probably due to increased dissolved oxygen (DO) coupled with low groundwater temperatures. Denitrifier functional genes were similar at all sites and depths. Data showed that highly favourable conditions prevailed for denitrification to occur--multiple electron donors, low redox potential (Eh<100 mV), low DO (<2 mg L⁻¹), low permeability (k(s)<0.005 m·d⁻¹) and a shallow unsaturated zone (<2 m). Quantification of excess N₂-N in groundwater helps to close N balances at the local, regional and global scales.

Impact of chemical amendment of dairy cattle slurry on phosphorus, suspended sediment and metal loss to runoff from a grassland soil.

Emerging remediation technologies such as chemical amendment of dairy cattle slurry have the potential to reduce phosphorus (P) solubility and consequently reduce P losses arising from land application of dairy cattle slurry. The aim of this study was to determine the effectiveness of chemical amendment of slurry to reduce incidental losses of P and suspended sediment (SS) from grassland following application of dairy cattle slurry and to examine the effect of amendments on metal concentrations in runoff water. Intact grassed-soil samples were placed in two laboratory runoff boxes, each 200-cm-long by 22.5-cm-wide by 5-cm-deep, before being amended with dairy cattle slurry (the study control) and slurry amended with either: (i) alum, comprising 8% aluminium oxide (Al(2)O(3)) (1.11:1 aluminium (Al):total phosphorus (TP) of slurry) (ii) poly-aluminium chloride hydroxide (PAC) comprising 10% Al(2)O(3) (0.93:1 Al:TP) (iii) analytical grade ferric chloride (FeCl(2)) (2:1 Fe:TP), (iv) and lime (Ca(OH)(2)) (10:1 Ca:TP). When compared with the study control, PAC was the most effective amendment, reducing dissolved reactive phosphorus (DRP) by up to 86% while alum was most effective in reducing SS (88%), TP (94%), particulate phosphorus (PP) (95%), total dissolved phosphorus (TDP) (81%), and dissolved unreactive phosphorus (DUP) (86%). Chemical amendment of slurry did not appear to significantly increase losses of Al and Fe compared to the study control, while all amendments increased Ca loss compared to control and grass-only treatment. While chemical amendments were effective, the reductions in incidental P losses observed in this study were similar to those observed in other studies where the time from slurry application to the first rainfall event was increased. Timing of slurry application may therefore be a much more feasible way to reduce incidental P losses. Future work must examine the long-term effects of amendments on P loss to runoff and not only incidental losses.

Use of Ochre from an Abandoned Metal Mine in the South East of Ireland for Phosphorus Sequestration from Dairy Dirty Water

Ochre found at coal mine drainage sites in the United Kingdom shows a high phosphorus (P) retention capacity with little mobilization of metals. This indicates that ochre has the potential to adsorb P from agricultural wastewaters for possible use as a fertilizer. Little research has focused on the ability of metal mine ochre to sequester P in an environmentally sustainable way. Untreated acid mine drainage from an abandoned copper-sulfur mine in the Avoca-Avonmore catchment in the south east of Ireland results in extensive low-value ochre deposition. In this study, P-amended water (50 mL) was mixed with this ochre (2.5 g) in batch experiments, and a maximum P adsorption capacity, calculated from the Langmuir equation, of between 16 and 21 g P kg(-1) was calculated. However, mobilization of heavy metals from Avoca ochre in distilled, surface, and dirty water batch experiments was observed. This mobilization may inhibit ochres use in P removal from wastewaters.

Storm Event Suspended Sediment-Discharge Hysteresis and Controls in Agricultural Watersheds: Implications for Watershed Scale Sediment Management

Within agricultural watersheds suspended sediment-discharge hysteresis during storm events is commonly used to indicate dominant sediment sources and pathways. However, availability of high-resolution data, qualitative metrics, longevity of records, and simultaneous multiwatershed analyses has limited the efficacy of hysteresis as a sediment management tool. This two year study utilizes a quantitative hysteresis index from high-resolution suspended sediment and discharge data to assess fluctuations in sediment source location, delivery mechanisms and export efficiency in three intensively farmed watersheds during events over time. Flow-weighted event sediment export was further considered using multivariate techniques to delineate rainfall, stream hydrology, and antecedent moisture controls on sediment origins. Watersheds with low permeability (moderately- or poorly drained soils) with good surface hydrological connectivity, therefore, had contrasting hysteresis due to source location (hillslope versus channel bank). The well-drained watershed with reduced connectivity exported less sediment but, when watershed connectivity was established, the largest event sediment load of all watersheds occurred. Event sediment export was elevated in arable watersheds when low groundcover was coupled with high connectivity, whereas in the grassland watershed, export was attributed to wetter weather only. Hysteresis analysis successfully indicated contrasting seasonality, connectivity and source availability and is a useful tool to identify watershed specific sediment management practices.

Incidental phosphorus and nitrogen loss from grassland plots receiving chemically amended dairy cattle slurry

Chemical amendment of dairy cattle slurry has been shown to effectively reduce incidental phosphorus (P) losses in runoff; however, the effects of amendments on incidental nitrogen (N) losses are not as well documented. This study examined P and N losses in runoff during three simulated rainfall events 2, 10 and 28 days after a single application of unamended/chemically amended dairy cattle slurry. Twenty-five hydraulically isolated plots, each measuring 0.9 m by 0.4 m and instrumented with runoff collection channels, were randomly assigned the following treatments: (i) grass-only, (ii) slurry-only (the study-control), (iii) slurry amended with industrial grade liquid alum comprising 8% Al₂O₃, (iv) slurry amended with industrial grade liquid poly-aluminum chloride (PAC) comprising 10% Al₂O₃, and (v) slurry amended with lime. During the first rainfall event, lime was ineffective but alum and PAC effectively reduced dissolved reactive P (DRP) (by 95 and 98%, respectively) and total P (TP) flow-weighted-mean-concentrations (by 82 and 93%, respectively) in runoff compared to the study-control. However, flow-weighted-mean-concentrations of ammonium-N (NH₄--N) in runoff were increased with alum- (81%) and lime-treated (11%) slurry compared to the study-control whereas PAC reduced the NH₄--N by 82%. Amendments were not observed to have a significant effect on NO₃--N losses during this study. Slurry amendments reduced P losses for the duration of the study, whereas the effect of amendments on N losses was not significant following the first event. Antecedent volumetric water content of the soil or slope of the plots did not appear to affect runoff volume. However, runoff volumes (and consequently loads of P and N) were observed to increase for the chemically amended plots compared to the control and soil-only plots. This work highlights the importance of considering both P and N losses when implementing a specific nutrient mitigation measure.

Barley (Hordeum vulgare)-induced growth inhibition of algae: a review.

Many field and laboratory studies have attempted to explain the inhibitory effect of rotting barley on algae. Early field studies lacked controls and replication and results depended on visual observations. Such studies offer information on barley bale field construction and application rates. In the laboratory, discrepancies in the barley variety used, algal species tested, barley liquor preparation and phenol extraction methodologies existed. Inconsistencies have led to different growth responses for the same species of algae tested, i.e. with some studies finding an inhibitory response and other studies reporting an accelerated growth response of algae. Two successful forms of investigation have been identified: (a) using commercially available compounds, i.e. with known shikimate-pathway-producing phenols and acids, which can then be combined with algal assays of different algal species and (b) using commercially available algal species from which batch cultures are grown, which are then added to barley liquor of different ages. Algal growth may then be investigated using in vivo fluorescence and the filtrate can be analysed via HPLC/MS. The identification of allelochemicals, which range from phenolics to quinones within the Poaceae family of which barley is a member, has received a lot of attention in recent years.

Consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates.

The true efficacy of a programme of agricultural mitigation measures within a catchment to improve water quality can be determined only after a certain hydrologic time lag period (subsequent to implementation) has elapsed. As the biophysical response to policy is not synchronous, accurate estimates of total time lag (unsaturated and saturated) become critical to manage the expectations of policy makers. The estimation of the vertical unsaturated zone component of time lag is vital as it indicates early trends (initial breakthrough), bulk (centre of mass) and total (Exit) travel times. Typically, estimation of time lag through the unsaturated zone is poor, due to the lack of site specific soil physical data, or by assuming saturated conditions. Numerical models (e.g. Hydrus 1D) enable estimates of time lag with varied levels of input data. The current study examines the consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates using simulated and actual soil profiles. Results indicated that: greater temporal resolution (from daily to hourly) of meteorological data was more critical as the saturated hydraulic conductivity of the soil decreased; high clay content soils failed to converge reflecting prevalence of lateral component as a contaminant pathway; elucidation of soil hydraulic properties was influenced by the complexity of soil physical data employed (textural menu, ROSETTA, full and partial soil water characteristic curves), which consequently affected time lag ranges; as the importance of the unsaturated zone increases with respect to total travel times the requirements for high complexity/resolution input data become greater. The methodology presented herein demonstrates that decisions made regarding input data and landscape position will have consequences for the estimated range of vertical travel times. Insufficiencies or inaccuracies regarding such input data can therefore mislead policy makers regarding the achievability of water quality targets.

Site-specific P absorbency of ochre from acid mine-drainage near an abandoned Cu-S mine in the Avoca–Avonmore catchment, Ireland

Abstract Acid mine-drainage from an abandoned Cu-S mine adit, located in the Avoca-Avonmore catchment in the southeast of Ireland, results in low-value ochre deposition. Ochre found on-site had similar physical (particle size 97.7% <2 mm and dry bulk density 0.8 g cm3), but dissimilar maximum P-retention characteristics (16-21 g P kg-1) to coal-mining ochre found in the UK. Stereomicroscopy identified oolites and diatoms in the ochre that were indicative of acidic environments. X-ray diffraction showed Fe mineralogy consisting of goethite, jarosite and minor amounts of ferrihydrite. Investigations by inductively coupled plasma-mass spectrometry and bulk energy-dispersive spectroscopy showed potentially toxic concentrations of Fe, Zn, Pb, As and Cu. Rapid mobilization of metals occurred during P-adsorption tests, which makes Avoca ochre unsuitable for use in a surface-water environmental technology.