Determination and occurrence of phenoxyacetic acid herbicides and their transformation products in groundwater using ultra high performance liquid chromatography coupled to tandem mass spectrometry.

A sensitive method was developed and validated for ten phenoxyacetic acid herbicides, six of their main transformation products (TPs) and two benzonitrile TPs in groundwater. The parent compounds mecoprop, mecoprop-p, 2,4-D, dicamba, MCPA, triclopyr, fluroxypr, bromoxynil, bentazone, and 2,3,6-trichlorobenzoic acid (TBA) are included and a selection of their main TPs: phenoxyacetic acid (PAC), 2,4,5-trichloro-phenol (TCP), 4-chloro-2-methylphenol (4C2MP), 2,4-dichlorophenol (DCP), 3,5,6-trichloro-2-pyridinol (T2P), and 3,5-dibromo-4-hydroxybenzoic acid (BrAC), as well as the dichlobenil TPs 2,6-dichlorobenzamide (BAM) and 3,5-dichlorobenzoic acid (DBA) which have never before been determined in Irish groundwater. Water samples were analysed using an efficient ultra-high performance liquid chromatography (UHPLC) method in an 11.9 min separation time prior to detection by tandem mass spectrometry (MS/MS). The limit of detection (LOD) of the method ranged between 0.00008 and 0.0047 µg·L(-1) for the 18 analytes. All compounds could be detected below the permitted limits of 0.1 µg·L(-1) allowed in the European Union (EU) drinking water legislation. The method was validated according to EU protocols laid out in SANCO/10232/2006 with recoveries ranging between 71% and 118% at the spiked concentration level of 0.06 µg·L(-1). The method was successfully applied to 42 groundwater samples collected across several locations in Ireland in March 2012 to reveal that the TPs PAC and 4C2MP were detected just as often as their parent active ingredients (a.i.) in groundwater.

Pesticide occurrence in groundwater and the physical characteristics in association with these detections in Ireland.

This study explores the associations of pesticide occurrence in groundwater to geological characteristics of the monitoring points (MPs) contributing area. Pesticide analyses were undertaken during a 2-year groundwater monitoring campaign which generated 845 samples. MCPA and mecoprop were the most frequently detected pesticides in groundwater. Each MP (n = 158) had a specifically delineated zone of contribution (ZOC) and the dominant physical characteristics present from nine national datasets were recorded for each ZOC. Associations between detections in groundwater and the dominant physical characteristic in each MPs ZOC tested were then statistically analyzed using Fisher's exact test, logistic regression, and multiple logistic regression. The original physical characteristic datasets used that were associated with detections in groundwater were the type of MP, aquifer type, and Quaternary deposit type. Logistic regression revealed that springs, regionally important aquifer types, aquifers with a karstic flow regime, and alkaline Quaternary deposits in existence above karst aquifers in a MP's ZOC were more likely to have a pesticide detection in groundwater. Multiple regression from this exploratory work showed some mutual dependency between soil association, aquifer type, and the Geological Survey of Ireland groundwater vulnerability map. The combination of national monitoring data and physical attribute datasets can be used to explore key areas where groundwater is more vulnerable to pesticide contamination.

Simplifying and improving the extraction of nitrate from freshwater for stable isotope analyses.

Determining the isotopic composition of nitrate (NO(3)(-)) in water can prove useful to identify NO(3)(-) sources and to understand its dynamics in aquatic systems. Among the procedures available, the 'ion-exchange resin method' involves extracting NO(3)(-) from freshwater and converting it into solid silver nitrate (AgNO(3)), which is then analysed for (15)N/(14)N and (18)O/(16)O ratios. This study describes a simplified methodology where water was not pre-treated to remove dissolved organic carbon (DOC) or barium cations (added to precipitate O-bearing contaminants), which suited samples with high NO(3)(-) (≥ 00 µM or 25 mg L(-1) NO(3)(-)) and low DOC (typically < 17 µM of C or 5 mg L(-1) C) levels. % N analysis revealed that a few AgNO(3) samples were of low purity (compared with expected % N of 8.2), highlighting the necessity to introduce quality control/quality assurance procedures for silver nitrate prepared from field water samples. Recommendations are then made to monitor % N together with % O (expected at 28.6, i.e. 3.5 fold % N) in AgNO(3) in order to better assess the type and gravity of the contamination as well as to identify potentially unreliable data.

Hydrogeological characteristics influencing the occurrence of pesticides and pesticide metabolites in groundwater across the Republic of Ireland.

Pesticide contamination of water is a potential environmental issue which may impact the quality of drinking water. The full extent of pesticide contamination is not fully understood due to complex fate pathways in the subsurface. Groundwater pesticide occurrence was investigated at seven agricultural sites in different hydrogeological settings to identify where pesticide occurrence dominated in temperate maritime climatic conditions. In Ireland, six cereal dominated sites in the South East and one grassland site in the West were investigated. Soil and subsoils varied from acid brown earths with high permeability to clay and silt rich tills with lower permeability. Over a 2year monitoring period, 730 samples were collected from a network of dedicated wells and springs across the seven sites. Multi-nested piezometers were installed in intergranular, fissured and karstic type aquifers to target shallow, transition and deeper groundwaters. Several springs were also sampled and the network included a confined aquifer. Groundwater was analysed for nine pesticide active ingredients and eight metabolites. Mecoprop and 2,4-D were the most frequently detected active ingredients above the instrument detection limit, accounting for 36% and 26% of the 730 samples collected and analysed. Phenoxyacetic acid was the most frequently detected and widespread metabolite found in 39% of samples collected at all seven sites. Where the European Union drinking water standard of 0.1µg/L was exceeded, metabolites accounted for the majority of exceedances with 3,5-dichlorobenzoic acid (DBA) and phenoxyacetic acid (PAC) dominating. Highest detections were encountered in sites with well drained soils underlain by gravel and limestone aquifers and within gravel lenses in lower permeability subsoil. Across the seven sites pesticide detections were mostly associated with metabolites and the environmental impact of many of these is unknown as they have received little attention in groundwater previously.

Effects of over-winter green cover on soil solution nitrate concentrations beneath tillage land.

There is a growing need to reduce nitrogen losses from agricultural systems to increase food production while reducing negative environmental impacts. The efficacy of vegetation cover for reducing nitrate leaching in tillage systems during fallow periods has been widely investigated. Nitrate leaching reductions by natural regeneration (i.e. growth of weeds and crop volunteers) have been investigated to a lesser extent than reductions by planted cover crops. This study compares the efficacy of natural regeneration and a sown cover crop (mustard) relative to no vegetative cover under both a reduced tillage system and conventional plough-based system as potential mitigation measures for reducing over-winter soil solution nitrate concentrations. The study was conducted over three winter fallow seasons on well drained soil, highly susceptible to leaching, under temperate maritime climatic conditions. Mustard cover crop under both reduced tillage and conventional ploughing was observed to be an effective measure for significantly reducing nitrate concentrations. Natural regeneration under reduced tillage was found to significantly reduce the soil solution nitrate concentrations. This was not the case for the natural regeneration under conventional ploughing. The improved efficacy of natural regeneration under reduced tillage could be a consequence of potential stimulation of seedling germination by the autumn reduced tillage practices and improved over-winter plant growth. There was no significant effect of tillage practices on nitrate concentrations. This study shows that over winter covers of mustard and natural regeneration, under reduced tillage, are effective measures for reducing nitrate concentrations in free draining temperate soils.

Quantitative solid phase microextraction - gas chromatography mass spectrometry analysis of the pesticides lindane, heptachlor and two heptachlor transformation products in groundwater.

This paper describes the development and validation of a method for the determination of lindane, heptachlor and two heptachlor transformation products (exo- and endo-heptachlor epoxide) in groundwater. Samples were extracted using a simple solid phase microextraction (SPME) method with a polyacrylate fibre prior to detection by gas chromatography mass spectrometry in electron impact ionisation mode (GC-EI-MS). The linearity of the method ranged from 0.015 to 5.0 µg L(-1), with correlation coefficients greater than 0.99. Recoveries ranged from 96 to 101% at several fortification levels with all coefficients of variation (CV%) less than 10.5%. The method was validated to the permitted limits laid down in the European Union drinking water directive (98/83/EC). The limit of quantitation (LOQ) was 0.015 µg L(-1) in groundwater samples. Samples had to be analysed within 24h of collection otherwise degradation occurred and disposable SPME polyacrylate fibres lasted up to 51 injections. Both endo-heptachlor epoxide and lindane were detected in groundwater samples with concentrations ranging between 0.033 and 0.048 µg L(-1).

Comparison of pesticide leaching potential to groundwater under EU FOCUS and site specific conditions.

The EU FOCUS scenarios are a set of nine standard scenarios based on a combination of crop, soil and weather data used throughout Europe to evaluate the leaching potential of pesticides to groundwater. In Ireland, two predefined EU FOCUS scenarios (Okehampton and Hamburg) appear to be the most appropriate to Irish conditions. However, there is concern that these scenarios may not accurately represent Irish specific conditions, especially in terms of soil and climatic weather. Therefore, the objective of this study was to parameterise a number of site specific locations in Ireland (represented by Oakpark, Clonroche, Rathangan and Elton series soils) and to compare simulated leachate levels at these locations to EU FOCUS scenarios using the PELMO (Pesticide Leaching Model) simulation model. The hydrological processes were validated using observed data for soil tension and leachate. The appropriate EU FOCUS scenarios were then simulated for the given locations and compared to the parameterised scenario. All scenarios were run using the same version of PELMO, therefore eliminating any software impacts. The models were run for 26 years using appropriate meteorological data. The results showed significant difference between the parameterised model pesticide leaching and that resulting from the EU FOCUS scenarios, the latter overestimating site pesticide leaching from 42 to 99%. The results indicated a significant conservatism in using EU FOCUS scenarios to determine potential pesticide concentration in the leachate under Irish specific conditions and ensure the desired level of protection against pesticide contamination of national water resources.

Effects of over-winter green cover on groundwater nitrate and dissolved organic carbon concentrations beneath tillage land.

Application of over-winter green cover (e.g. cover crops) as a measure for reducing nitrate losses from tillage land has been frequently investigated, especially in the unsaturated zone. Monitoring of groundwater is less common in these studies. Studies on groundwater responses to different land treatments can be challenging because they can be influenced by various conditions, such as recharge, seasonal variations, and aquifer properties, often occurring at different time scales than surface water processes. The aim of this study was to evaluate groundwater nitrate (NO(3)(-)N) and dissolved organic carbon (DOC) concentration responses to different over-winter green covers: mustard, natural regeneration and no cover. A field experiment was designed and run for three years on tillage land underlain by a vulnerable sand and gravel aquifer in the south-east of Ireland. Results showed that over-winter green cover growth on tillage land can be an effective measure to reduce groundwater NO(3)(-)N concentrations. A significant decrease in groundwater NO(3)(-)N concentrations was observed under the mustard cover compared to no cover. All treatments, including no cover, showed a decline in groundwater NO(3)(-)N concentrations over time. A significant increase in groundwater DOC was also observed under the mustard cover. Although the overall groundwater DOC concentrations were low, the increased DOC occurrence in groundwater should be accounted for in carbon balances and could potentially enhance groundwater denitrification in cases where aquifer conditions may favour it.