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A groundwater monitoring network surrounding a pumping well (such as a public water supply) allows for early contaminant detection and mitigation where possible contaminant source locations are often unknown. This numerical study investigates how the contaminant detection probability of a hypothetical sentinel-well monitoring network consisting of one to four monitoring wells is affected by aquifer spatial heterogeneity and dispersion characteristics, where the contaminant source location is randomized. This is achieved through a stochastic framework using a Monte Carlo approach. A single production well is considered that results in converging non-uniform flow close to the well. Optimal network arrangements are obtained by maximizing a weighted risk function that considers true and false positive detection rates, sampling frequency, early detection, and contaminant travel time uncertainty. Aquifer dispersivity is found to be the dominant parameter for the quantification of network performance. For the range of parameters considered, a single monitoring well screening the full aquifer thickness is expected to correctly and timely identify at least 12% of all incidents resulting in contaminants reaching the production well. This proportion increases to a global maximum of 96% for a network consisting of four wells and very dispersive transport conditions. Irrespective of network size and sampling frequency, more dispersive transport conditions result in higher detection rates. Increasing aquifer heterogeneity and decreasing aquifer spatial continuity also lead to higher detection rates, though these effects are diminished for networks of 3 or more wells. Statistical anisotropy has no effect on the network performance. Earlier detection, which is critical for remedial action and supply safety, comes with a significant cost in terms of detection rate, and should be carefully considered when a monitoring network is being designed.

The vast majority of microorganisms in aquifers live as biofilms on sediment surfaces, which presents significant challenges for sampling as only the suspended microbes will be sampled through normal pumping. The use of a down-well low frequency sonicator has been suggested as a method of detaching microbes from the biofilm and allowing rapid sampling of this community. We developed a portable, easy to use, low-frequency electric sonicator and evaluated its performance for a range of well depths (tested up to 42 m below ground level) and casing types. Three sonicators were characterized in laboratory experiments using a 1 m long tank filled with pea gravel. These included a commercially available pneumatic sonicator, a rotating flexible shaft sonicator, and the prototype electric sonicator. The electric sonicator detached between 56 and 74% of microbes grown on gravel-containing biobags at distances ranging between 2 and 50 cm from the sonicator. The field testing comprises of a total of 55 sampling events from 48 wells located in 4 regions throughout New Zealand. Pre- and post-sonication samples showed an average 33 times increase in bacterial counts. Microbial sequence data showed that the same classes are present in pre- and post-sonicated samples and only slight differences were seen in the proportions present. The sampling process was rapid and the significant increases in bacterial counts mean that microbial samples can be quickly obtained from wells, which permits more detailed analysis than previously possible.

Diffuse nitrate leaching from agricultural areas is a major environmental problem in many parts of the world. Understanding where in a catchment nitrate is removed is key for designing effective land use management strategies that protect water quality, while minimizing the impact on economic development. In this study we assess the effects of spatially targeted nitrate leaching regulation in a basin with limited knowledge of the complexity of chemical heterogeneity. Three alternative nitrate reactivity spatial parameterizations were incorporated in a catchment-scale flow and transport model and used to evaluate the effectiveness of four possible spatially targeted regulation options. Our findings confirm that denitrification parameterization cannot be numerically determined based on model inversion alone. Detailed field based characterization using physical and geochemical methods should be considered and incorporated in the numerical inversion scheme. We also demonstrate that there are potential benefits of implementing spatially targeted regulation compared to spatially uniform regulation. Focusing regulation in areas where nitrate residence time is short, such as riparian zones or areas with low natural N-reduction, results in greater reduction of N-discharges through groundwater. Significantly improved efficiencies can be expected when delineation of management zones considers the chemical heterogeneity and groundwater flow paths. These improved efficiencies are achieved by adopting management rules that regulate land use in discharge sensitive areas, where leaching changes contribute the most to the catchment nitrate discharges. In our case study, regulation in discharge sensitive zones was twice as efficient compared to other management options.

Spatially distributed nitrate reactivity was estimated for the alluvial aquifer system within the Ruamāhanga catchment in New Zealand, according to the groundwater redox status, integrating machine learning and physically based modelling approaches. Redox classification was carried out for sampled groundwater, and linear discriminant analysis (LDA) was used to spatially discriminate between three redox classes across the catchment, using mappable physical parameters as predictive variables. The LDA model predictive uncertainty was used to quantify the spatially distributed geochemical uncertainty of the denitrification potential. Nitrate reduction was simulated as first order irreversible reaction using MT3DMS. Using a Monte Carlo approach, where random redox status realizations were aggregated to various model spatial discretization scales and each transport model realization was re-calibrated, we assessed the relationship between lower order nitrate reduction parameter statistics and aggregation scale. Our results indicate that both the average nitrate reduction parameter values and their standard deviations increase with increased spatial scale. This suggests that the parameters used to model denitrification as first-order reduction in geochemically heterogeneous environments, depend on the geochemical heterogeneity scale. This can have implications when knowledge gained at local scales needs to be applied for basin-scale assessment of effects. Similar were our findings with regards to the parameter-scale dependency on the model predictive uncertainty. Even though the average nitrate reduction across the model domain did not vary with redox scale, the standard deviation around the average almost doubled between the 250 and 5000 m scales.

A hydrological framework encompassing nitrogen (N), phosphorus (P) and microbial (E. coli) transfer from land to water was developed to provide a consistent and rapid approach for assessing the potential impacts of land activity on water quality in New Zealand. A flow partition approach was used to route precipitation via surface and subsurface pathways from land to water. The framework included a typology-based inventory that estimates annual yields of transportable N and P from land, a regional-scale spatial layer that attenuates N in groundwater, and literature-based estimates of E. coli concentrations in surface runoff and artificial drainage. Application of the framework in four catchments highlighted the importance of local catchment knowledge of dominant hydrological processes that was needed to ensure flow partitions derived were a realistic representation of transport processes. While the approach was promising, additional refinements are needed to improve process representation (e.g. effects of groundwater lags) and ensure input data (e.g. soil attributes) have appropriate resolution to describe hydrological pathways. We contend that such a framework would provide a consistent and relatively rapid approach for identifying contaminant transfer pathways from land to water that can inform assessments of the potential consequences of land use change and intensification.

Monte Carlo uncertainty analysis, model calibration and optimization applications in hydrology, usually involve a very large number of forward transient model solutions, often resulting in computational bottlenecks. Parallel processing can significantly reduce overall simulation time, benefiting from the architecture of modern computers. This work investigates system performance using two realistic flow and transport modeling scenarios, applied to various modeling hardware, to provide information on the expected performance of parallel simulations and inform investment decisions. We investigate how performance, measured in terms of speedup and efficiency, changes with increasing number of parallel processes. We conclude that the maximum performance achieved by parallelization can range from 40% to 100% of the theoretical limit, with the lower increases associated with multi-CPU servers. The number of parallel processes required to maximize performance is application dependent, and in contrast to common practice, often needs to be significantly larger than the total number of system CPU cores. Further testing is required to better understand how the physical problem being simulated affects the optimal number of parallel processes needed. Finally, when laptops are considered for modeling applications, careful consideration should be given not only to the specifications but also to the intended use designated by the manufacturer.

A test using Rhodamine WT and heat as tracers, conducted over a 78 day period in a strongly heterogeneous alluvial aquifer, was used to evaluate the utility of the combined observation dataset for aquifer characterization. A highly parameterized model was inverted, with concentration and temperature time-series as calibration targets. Groundwater heads recorded during the experiment were boundary dependent and were ignored during the inversion process. The inverted model produced a high resolution depiction of the hydraulic conductivity and porosity fields. Statistical properties of these fields are in very good agreement with estimates from previous studies at the site. Spatially distributed sensitivity analysis suggests that both solute and heat transport were most sensitive to the hydraulic conductivity and porosity fields and less sensitive to dispersivity and thermal distribution factor, with sensitivity to porosity greatly reducing outside the monitored area. The issues of model over-parameterization and non-uniqueness are addressed through identifiability analysis. Longitudinal dispersivity and thermal distribution factor are highly identifiable, however spatially distributed parameters are only identifiable near the injection point. Temperature related density effects became observable for both heat and solute, as the temperature anomaly increased above 12 degrees centigrade, and affected down gradient propagation. Finally we demonstrate that high frequency and spatially dense temperature data cannot inform a dual porosity model in the absence of frequent solute concentration measurements.

Diffuse nitrate losses from agricultural land pollute groundwater resources worldwide, but can be attenuated under reducing subsurface conditions. In New Zealand, the ability to predict where groundwater denitrification occurs is important for understanding the linkage between land use and discharges of nitrate-bearing groundwater to streams. This study assesses the application of linear discriminant analysis (LDA) for predicting groundwater redox status for Southland, a major dairy farming region in New Zealand. Data cases were developed by assigning a redox status to samples derived from a regional groundwater quality database. Pre-existing regional-scale geospatial databases were used as training variables for the discriminant functions. The predictive accuracy of the discriminant functions was slightly improved by optimising the thresholds between sample depth classes. The models predict 23% of the region as being reducing at shallow depths ( The regional scale model predictions indicate that subsurface reducing conditions predominate at low elevations on the coastal plains where poorly drained soils are widespread. Additional indicators for subsurface denitrification are a high carbon content of the soil, a shallow water table, and low-permeability clastic sediments. The coastal plains are an area of widespread groundwater discharge, and the soil and hydrology characteristics require the land to be artificially drained to render the land suitable for farming. For the improvement of water quality in coastal areas, it is therefore important that land and water management efforts focus on understanding hydrological bypassing that may occur via artificial drainage systems.

Potable groundwater contamination by human enteric viruses poses serious health risks. Our understanding of virus subsurface transport has largely depended on studying bacteriophages as surrogates. Few studies have compared the transport behaviour of enteric viruses, especially norovirus, with phage surrogates. We conducted laboratory column experiments to investigate norovirus and bacteriophage MS2 (MS2) filtration in alluvial sand, and rotavirus, adenovirus and MS2 filtration in alluvial gravel aquifer media in 2 mM NaCl (pH 6.6–6.9) with pore velocities of 4.6–5.4 m/day. The data were analysed using colloid filtration theory and HYDRUS-1D 2-site attachment-detachment modelling. Norovirus removal was somewhat lower than MS2 removal in alluvial sand. The removal of rotavirus and adenovirus was markedly greater than MS2 removal in alluvial gravel. These findings concurred with the log10 reduction values, mass recoveries, attachment efficiencies and irreversible deposition rate constants. The modelling results suggested that the MS2 detachment rates were in the same order of magnitude as norovirus, but they were 1 order of magnitude faster than those of rotavirus and adenovirus. The attachment of viruses and MS2 was largely reversible with faster detachment than attachment rates, favouring free virus transport. These findings highlight the risk associated with continual virus transport through subsurface media if viruses are not inactivated and remobilising previously attached viruses could trigger contamination events. Thus, virus attachment reversibility should be considered in virus transport predictions in subsurface media. Further research is needed to compare surrogates with enteric viruses, especially norovirus, regarding their transport behaviours under different experimental conditions.

Open framework gravels (OFGs) are an inherent textural component of alluvial gravel outwash deposited by braided river systems. Being exceptionally permeable, they play an important part in facilitating the transmission of water and contaminants through alluvial gravel aquifers. Understanding how connected OFG facies are is helpful in making informed predictions about groundwater flow and contaminant transport through such aquifer systems. This work examined a section of the Rakaia fan, Canterbury, New Zealand. A 3×3 grid of large diameter auger holes was drilled in close proximity to a sea cliff, which provided very good three-dimensional exposure of the fan architecture. A novel smoke tracing experiment and water tracing field tests were conducted to measure the dynamic connectivity of the OFG facies. Smoke proved to be an effective tracer for measuring the interconnectedness of OFGs over set distances of 5 m. The water tracing tests confirmed that OFGs are connected across much longer distances – in excess of 18 m. Results from both tests revealed how rapid, and non-uniform, aqueous transport can be through alluvial outwash materials. The connectivity information will be used to improve realizations of the heterogeneity of the Canterbury Plains aquifer and inform future hydrogeological modelling.

An important policy consideration for integrated land and water management is to understand the spatial distribution of nitrate attenuation in the groundwater system, for which redox condition is the key indicator. This paper proposes a methodology to accommodate the computational demands of large datasets, and presents national-scale predictions of groundwater redox class for New Zealand. Our approach applies statistical learning methods to relate the redox class determined on groundwater samples to spatially varying attributes. The trained model uses these spatial variables to predict redox status in areas without sample data. We assembled the groundwater sample data from regional authority databases, and assigned each sample a redox class. A key achievement was to overcome the influence of sample selection bias on model training via oversampling. We removed additional bias imposed by imbalances in the predictor variables by applying a conditional inference random forest classifier. The unbiased trained model uses eight predictors, and achieves a high validation performance (accuracy 0.81, kappa 0.71), providing good confidence in model predictions. National maps are provided for redox class and probability at specified depths. Feature importance rankings indicate that reducing conditions are associated with poorly-drained soils, and to a lesser extent, high hydrological variability, low elevation, and low-permeability lithology. These conditions are common in New Zealand's coastal and lowland plains, where artificial drainage is required to make land suitable for production. The spatial extent of reduced groundwater increases with depth, suggesting a shallow influence of soil infiltration or mobile organic carbon, and a deeper influence of lithological electron donors. Our model provides unbiased predictions at a scale relevant for environmental policy development and legislation. Identifying where the ecosystem service provided by denitrification can be utilised will enable spatially targeted interventions that can achieve the desired environmental outcome in a more cost-effective manner than non-targeted interventions.

Rising demand on food is leading to an increase in irrigation worldwide to improve productivity. Irrigation, for pastoral agriculture (beef, dairy and sheep), is the largest consumptive use of water in New Zealand. There is a potential risk of leaching of microbial contaminants from faecal matter through the vadose zone into groundwater. Management of irrigation is vital for protection of groundwater from these microbial contaminants and maintain efficient irrigation practices. Our research investigated flood and spray irrigation, two practices common in New Zealand. The aim was to identify the risk of microbial transport and mitigation practices to reduce or eliminate the risk of microbial transport into groundwater. Cowpats were placed on lysimeters over a typical New Zealand soil (Lismore silt loam) and vadose zone and the leachate collected after irrigation events. Samples of both cowpats and leachate were analysed for the microbial indicator Escherichia coli and pathogen Campylobacter species. A key driver to the microbial transport derived from the model applied was the volume of leachate collected: doubling the leachate volume more than doubled the total recovery of E. coli. The persistence of E. coli in the cowpats during the experiment is an important factor as well as the initial environmental conditions, which were more favourable for survival and growth of E. coli during the spray irrigation compared with the flood irrigation. The results also suggest a reservoir of E. coli surviving in the soil. Although the same was potentially true for Campylobacter, little difference in the transport rates between irrigation practices could be seen due to the poor survival of Campylobacter during the experiment. Effective irrigation practices include monitoring the irrigation rates to minimise leachate production, delaying irrigation until 14 days post-cowpat deposition and only irrigating when risk of transport to the groundwater is minimal.Aim: To compare the risk of microbial contamination of groundwater from cowpats using two irrigation practices onto pasture.

The first national survey of Emerging Organic Contaminants (EOCs) involved sampling 121 wells located throughout New Zealand and analysis for a suite of 29 EOCs. This survey was carried out in conjunction with the 2018 national survey of pesticides in groundwater, a survey that is conducted on a four-yearly basis which included the analysis of glyphosate for first time. A total of 227 EOCs were detected in the 85 wells (70%). There were 29 different EOCs in the analytical suite and 25 different EOCs were detected in at least one well. The highest concentration measured was 655 ng/L for sucralose, an artificial sweetener. These results indicate that EOCs, sourced from either animal or human effluents/activities, are making their way into shallow groundwater systems and can be detected at low concentrations. A total of 135 wells were analysed for glyphosate, glufosinate and their principal metabolites. There was only one detection of glyphosate at a concentration of 2.1 μg/L. This well showed evidence of poor wellhead protection and the contamination likely came from containers that were stored near the well. A total of 279 wells were sampled and analysed for pesticides and 68 wells (24.4%) contained detectable residues of pesticides, with 28 of these wells having two or more pesticides detected. The maximum number of pesticides detected in one well was six. None of the sampled wells exceeded the Maximum Acceptable Value (MAV) for drinking water in New Zealand and the concentrations of most of the detected pesticides were equivalent to less than 0.5% of the MAV. Comparisons with earlier National Surveys of pesticides in groundwater in New Zealand indicate the frequencies of pesticide detections have remained similar over the last 16 years, with higher detection frequencies occurring before that time.

Reducing conditions are necessary for denitrification, thus the groundwater redox status can be used to identify subsurface zones where potentially significant nitrate reduction can occur. Groundwater chemistry in two contrasting regions of New Zealand was classified with respect to redox status and related to mappable factors, such as geology, topography and soil characteristics using discriminant analysis. Redox assignment was carried out for water sampled from 568 and 2223 wells in the Waikato and Canterbury regions, respectively. For the Waikato region 64% of wells sampled indicated oxic conditions in the water; 18% indicated reduced conditions and 18% had attributes indicating both reducing and oxic conditions termed "mixed". In Canterbury 84% of wells indicated oxic conditions; 10% were mixed; and only 5% indicated reduced conditions. The analysis was performed over three different well depths,25m, 25 to 100 and100m. For both regions, the percentage of oxidised groundwater decreased with increasing well depth. Linear discriminant analysis was used to develop models to differentiate between the three redox states. Models were derived for each depth and region using 67% of the data, and then subsequently validated on the remaining 33%. The average agreement between predicted and measured redox status was 63% and 70% for the Waikato and Canterbury regions, respectively. The models were incorporated into GIS and the prediction of redox status was extended over the whole region, excluding mountainous land. This knowledge improves spatial prediction of reduced groundwater zones, and therefore, when combined with groundwater flow paths, improves estimates of denitrification.

Phosphorous (P) leaching (e.g., from effluents, fertilizers) and transport in highly permeable subsurface media can be an important pathway that contributes to eutrophication of receiving surface waters as groundwater recharges the base-flow of surface waters. Here we investigated attenuation and transport of orthophosphate-P in gravel aquifer and vadose zone media in the presence and absence of model colloids (Escherichia coli, kaolinite, goethite). Experiments were conducted using repacked aquifer media in a large column (2m long, 0.19m in diameter) and intact cores (0.4m long, 0.24m in diameter) of vadose zone media under typical field flow rates. In the absence of the model colloids, P was readily traveled through the aquifer media with little attenuation (up to 100% recovery) and retardation, and P adsorption was highly reversible. Conversely, addition of the model colloids generally resulted in reduced P concentration and mass recovery (down to 28% recovery), and increased retardation and adsorption irreversibility in both aquifer and vadose zone media. The degree of colloid-assisted P attenuation was most significant in the presence of fine material and Fe-containing colloids at low flow rate but was least significant in the presence of coarse gravels and E. coli at high flow rate. Based on the experimental results, setback distances of 49-53m were estimated to allow a reduction of P concentrations in groundwater to acceptable levels in the receiving water. These estimates were consistent with field observations in the same aquifer media. Colloid-assisted P attenuation can be utilized to develop mitigation strategies to better manage effluent applications in gravelly soils. To efficiently retain P within soil matrix and reduce P leaching to groundwater, it is recommended to select soils that are rich in iron oxides, to periodically disturb soil preferential flow paths by tillage, and to apply a low irrigation rate.

Woodchip denitrification walls are a tried and tested groundwater nitrate remediation concept in shallow sandy aquifer conditions. There are however no published case studies of them having been applied in heterogeneous, fast-flowing gravel aquifers. Such a pilot study is being made in a shallow alluvial gravel aquifer on the Canterbury Plains, New Zealand, as part of an assessment of whether denitrification walls represent a viable edge-of-field nitrate mitigation option for the New Zealand hydrological landscape. Hydrogeological conditions at the field study site were characterised using a suite of investigative methods, the results from which informed design and placement of an experimental woodchip denitrification wall that was installed in November 2018. The average specific flux in the target gravel aquifer is estimated at 2.7 m/d, and 3.1 m/d through the woodchip wall itself, owing to its hydraulic efficiency. These groundwater fluxes are significantly higher than conditions reported for pre-existing denitrification wall case-studies. Monitoring of the groundwater chemistry over the first year of the denitrification woodchip wall's operational life has shown how the woodchip initially leached labile dissolved organic carbon and created a redox plume in which methanogenic conditions existed. Even though dissolved organic carbon concentrations have restored to background levels, the woodchip wall remains effective at nitrate reduction. The measured nitrate removal rate of between 4.2 and 5.4 g N removed/m3 wall/d is higher than what had previously been predicted from controlled lab-scale studies of the wall media and ranks towards the higher end of published removal rates for denitrification walls. Whilst there is direct evidence that heterotrophic denitrification is contributing to the observed nitrate removal, on the basis of chemical indicators, it is assumed other reactive process, such as dissimilatory reduction to ammonia, anammox, and possibly nitrate-reducing Fe(II)-oxidising reduction reactions may also be contributing to the overall removal of nitrogen in the system. Indications are the woodchip wall is enhancing emission of methane gas, albeit at rates less than what is typically reported for constructed wetlands that are an alternative nitrate-remediation option. Emission of the more potent greenhouse gas nitrous oxide from the woodchip denitrification wall has so far been immeasurably low. Longer-term study of the woodchip denitrification wall is continuing.

Groundwater is used as a precious resource for drinking water worldwide. Increasing anthropogenic activity is putting increasing pressure on groundwater resources. One impact of increased groundwater abstraction coupled with increasing dry weather events is the lowering of groundwater levels within aquifers. Biofilms within groundwater aquifers offer protection to the groundwater by removing contaminants entering the aquifer systems from land use activities. The study presented investigated the impact of desiccation events on the biofilms present in groundwater aquifers using field and laboratory experiments. In both field and laboratory experiments a reduction in enzyme activity (glucosidase, esterase and phosphatase) was seen during desiccation compared to wet controls. However, comparing all the data together no significant differences were seen between either wet or desiccated samples or between the start and end of the experiments. In both field and laboratory experiments enzyme activity recovered to start levels after return to wet conditions. The study shows that biofilms within groundwater systems are resilient and can withstand periods of desiccation (4 months).

Five re-circulating tracer well tests (RCTWTs) have been conducted in a variety of aquifer settings, at four sites across New Zealand. The tests constitute the first practical assessment of the two-well RCTWT methodology described by Burbery and Wang (Journal of Hydrology, 2010; 382:163–173) and were aimed at evaluating nitrate reaction rates in situ. The performance of the RCTWTs differed significantly at the different sites. The RCTWT method performed well when it was applied to determine potential nitrate reaction rates in anoxic, electro-chemically reductive, nitrate-free aquifers of volcanic lithology, on the North Island, New Zealand. Regional groundwater flow was not fast-flowing in this setting. An effective first-order nitrate reaction rate in the region of 0.09 d − 1 to 0.26 d − 1 was determined from two RCTWTs applied at one site where a reaction rate of 0.37 d − 1 had previously been estimated from a push–pull test. The RCTWT method performed poorly, however, in a fast-flowing, nitrate-impacted fluvio-glacial gravel aquifer that was examined on the South Island, New Zealand. This setting was more akin to the hypothetical physiochemical problem described by Burbery and Wang (2010) . Although aerobic conditions were identified as the primary reason for failure to measure any nitrate reaction in the gravel aquifer, failure to establish significant interflow in the re-circulation cell due to the heterogeneous nature of the aquifer structure, and natural variability exhibited in nitrate contaminant levels of the ambient groundwater further contributed to the poor performance of the test. Our findings suggest that in practice, environmental conditions are more complex than assumed by the RCTWT methodology, which compromises the practicability of the method as one for determining attenuation rates in groundwater based on tracing ambient contaminant levels. Although limited, there appears to be a scope for RCTWTs to provide useful information on potential attenuation rates when reactants are supplemented to the aquifer system under examination.

Subsoil denitrification is a potential sink for leached nitrate (NO₃–) that may otherwise contaminate ground water. A field trial was undertaken to assess the importance of subsoil denitrification and to examine the role of leached NO₃– on subsurface nitrous oxide (N₂O) (a potent greenhouse gas) dynamics. We monitored NO₃–, Br–, N₂O, CO₂, and O₂ concentrations in alluvial vadose materials to a depth of 7 m over a 32-mo period following the application of N (400 kg ha⁻¹ as NH₄NO₃) and Br– to potatoes (Solanum tuberosum L.) followed by a second application (400 kg ha⁻¹ as NH₄NO₃) to ryegrass (Lolium multiflorum Lam.) 24 mo later. Our sampling system consisted of an array of ceramic cups and permeable silicone tubing chambers to sample soil solution and gases. Following rainfall and irrigation, subsoil N₂O concentrations increased rapidly. Within days of NO₃– leaching below 1 m, high concentrations of NO₃–, Br–, and N₂O were observed at 7-m depth. Based on N to Br– ratios, and NO₃– leaching estimates from drainage amounts and leachate NO₃– concentrations, 5 to 10% of the fertilizer and soil N was denitrified. Based on N₂O flux estimates and NO₃––N/Br– ratios, almost all of the net N₂O production occurred in the subsoil above the gravel material (1-m depth). In the gravel matrix the NO₃––N/Br– ratio did not change indicating a low capacity to attenuate NO₃–.

The relative transport and attenuation of bacteria, bacteriophages, and bromide was determined in a 5 m long × 0.3 m diameter column of saturated, heterogeneous gravel. The average pore velocity (V), longitudinal dispersivity (α x ), and total removal rate (λ) were derived from the breakthrough curves at 1, 3, and 5 m, at a flow rate of 24.8 L h−1. The experiments largely confirmed the differences in transport and attenuation patterns among bacteria, phages, and bromide, and between colloid-associated and “free” microorganisms, previously observed in a study using homogeneous pea gravel. Cultured Escherichia coli J6-2 cells were transported faster than phage MS2 and bromide, consistent with velocity enhancement of the larger particles. The evidence for velocity enhancement of phage MS2 compared with bromide was less conclusive, with some evidence of retardation of the phage as a result of adsorption–desorption processes in the finer media. On average, phage in sewage and adsorbed to kaolin particles were transported faster than free phage, suggesting that most sewage phage are adsorbed to colloids. However, average velocities of cultured and sewage E. coli differed far less, suggesting that most E. coli in sewage exist as individual (non colloid-associated) cells. There was no conclusive evidence that the wider pore size range in the heterogeneous mixture compared with pea gravel increased velocity enhancement effects. Removal rates of free phage were far higher than in the pea gravel, and were attributed to adsorption in the finer materials. Equivalent increases in removal of cultured and sewage E. coli and colloid-associated phage were attributed to straining in finer materials and settling in quiescent zones. Inactivation (μ) rates (determined in the pea gravel study) indicated little contribution to removal of either free or attached microorganisms. The results showed the importance of association with colloids in determining the relative transport of bacteria and viruses in alluvial gravels.

To be able to predict contaminant transport in groundwater, an accurate conceptual and physical understanding of aquifer properties at multiple scales is required. In this study, physical and hydraulic properties of a coastal sand aquifer were derived using micro and macro X-ray computed tomography (XCT) techniques. Qualitative and quantitative data improved conceptualisation of the aquifer structure at micro and macro scale. At the macro scale (50-mm diameter by 1,500-mm long core) XCT images of undisturbed drill core identified coarse grained laminae (not obvious to the naked eye) of increased porosity and permeability, variations in mineral assemblage and particulate organic matter distribution within the core. Micro-XCT analysis (16-mm diameter cores) of the three main aquifer layers provided quantitative micro-scale data on permeability, porosity, grain, pore and throat size distribution statistics, and grain sphericity. Ratios of mean pore to grain diameter were ~0.65–0.75 and ratios of mean throat to mean grain diameter were ~0.2. Multiple permeability and porosity values were derived from micro domains (~4.35 mm3) within each micro-XCT core. Permeability values varied between and within micro-XCT core samples reflecting the heterogeneity at the millimetre core scale in these sediments. Sphericity values were similar for all three layers (average ~0.4) which reflected SEM observations of the semi-spherical nature of the dominant quartz and feldspar grains. The results of this study indicate that models based on the assumptions of homogeneity in depositional structure below centimetre scale may not suitably address factors affecting flow and transport of contaminants.

Understanding solute transport and flux through the vadose zone is important for predicting potential contaminant loading to groundwater systems. Two dual-permeability models: mixing cell (MC) and HYDRUS 1D (H1D DP ) were used to simulate long-term nonequilibrium Br − leaching using data derived from suction cup samples at two field sites (sampled to 7- and 4-m depths) on the Canterbury Plains, New Zealand. Effective model parameters were derived by inverse methods to represent average transport processes through the heterogeneous profiles. Suction cup samples indicated rapid initial movement of solute through the profiles followed by a long tail. The “management type” MC model results were comparable to the more complex HYDRUS model, providing similar overall fits to the observed data (similar RMSE ∼ 0.05–0.1). Modeling indicated that macropore flux was significant in transporting solute through the profile (MC range 5–59%; H1D DP range 15–54% of total fluxes) and simulations of cumulative fluxes from both models were similar. The MC model results indicated macropore transporting water contents of ∼0.003 (v/v) and matrix domain transporting water contents of around 0.1 to 0.15 (v/v) for the two field sites. These estimates suggest that only 3 mm of bulk drainage is required to transport solutes 1 m through the macropore domain, whereas approximately 100 to 150 mm of drainage is required to transport solutes the same distance through the matrix domain. More accurate representation of boundary conditions, texture spatial distributions, and hydraulic interactions is important for obtaining a better understanding of flux dynamics in future studies.

Viruses are often associated with colloids in wastewater and could be transported with colloids into groundwater from land disposal of human and animal effluent and sludge, causing contamination of groundwater. To investigate the role of colloids in the transport of viruses in groundwater, experiments were conducted using a 2m long column packed with heterogeneous gravel aquifer media. Bacteriophage MS2 was used as the model virus and kaolinite as the model colloid. Experimental data were analyzed using Temporal Moment Analysis and Filtration Theory. In the absence of kaolinite colloid, MS2 phage traveled slightly faster than the conservative tracer bromide (Br), with little differences observed between unfiltered and filtered MS2 phage (0.22 microm as the operational cut-off for colloid-free virus). In the presence of kaolinite colloids, MS2 phage breakthrough occurred concurrently with that of the colloidal particles and the time taken to reach the peak virus concentration was reduced, suggesting a colloid-facilitated virus transport in terms of peak-concentration time and velocity. Meanwhile mass recovery and magnitude of concentrations of the phages were significantly reduced, indicating colloid-assisted virus attenuation in terms of concentrations and mass. Decreasing the pH or increasing the ionic strength increased the level of virus attachment to the aquifer media and colloids, and virus transport became more retarded, resulting in lower peak-concentration, lower mass recovery, longer peak-concentration time, and greater apparent collision efficiency. Increasing the concentration of dissolved organic matter (DOM) or flow rate resulted in faster virus transport velocity, higher peak-concentrations and mass recoveries, and lower apparent collision efficiencies. The dual-role of colloids in transport viruses has important implications for risk analysis and remediation of virus-contaminated sites.

Understanding the physical and hydraulic properties of the vadose zone is important for modeling land use effects on groundwater quality. This study used a variety of characterization methods to derive conceptual understanding and estimates of hydraulic properties of a coarse alluvial gravel vadose zone in New Zealand. Sandy gravel (SG) material constituted approximately 90% of the vadose zone, with the remainder comprising sand lenses and open-framework gravels. The gravel content of the SG material was approximately 70% (v/v) (range 68–73%). The water content of the bulk SG material (43 samples) ranged from 3.5 to 13.9%. The average bulk density of the SG material was 2.20 g/cm 3 (range 2.00–2.33 g/cm 3 ) giving an average calculated porosity of 17%. The average porosity of the open-framework gravels was 34% and these gravels were often coated with 2- to 3-mm-thick deposits of amorphous Fe and Mn oxides. Neutron probe (NP) depth profiles indicated unsteady conditions, with variable water contents with depth and time reflecting the vertical heterogeneity and the variably saturated state of the vadose zone. Time series NP data to 3 m indicated water content in the alluvial gravels responded quickly to soil drainage events, and saturation variability was greater in the sand lenses and the SG material immediately underlying. When compared with derived water retention curves, variability in the water content equated to significant fluctuation in unsaturated hydraulic conductivity ( K unsat ). Tension infiltrometer measurements were variable but were within the range of the K unsat estimates from site-average particle size distribution data. The gravel-transformed, texture-based models used to estimate saturated water content values in this study appeared to underestimate the measured values.

We used three non-linear bi-phasic models, bi-exponential (BEXP), first-order double exponential decay (FODED), and first-order two-compartment (FOTC), to fit the measured degradation data for six commonly used pesticides (atrazine, terbuthylazine, bromacil, diazinon, hexazinone and procymidone) in two New Zealand soils. Corresponding DT50 and DT90 values for each compound were numerically obtained and compared against those estimated by simple first-order kinetic (SFOK) model. All 3 non-linear models gave good fit of the measured data under both soil depths and were well supported by the values obtained for the respective statistical indices (RMSE, CRM and r 2). The FOTC model gave by far the best fit for most compounds, followed by the FODED and BEXP models. Overall, DT50 values derived by non-linear models for the six compounds in soils from both sites were lower than the values obtained by the SFOK model. Differences in the SFOK and the three non-linear models derived DT90were, however, an order of ma...

The ability to quantify the mass flux of a groundwater contaminant that is leaching from a source area is critical to enable us to: (1) evaluate the risk posed by the contamination source and prioritize cleanup, (2) evaluate the effectiveness of source remediation technologies or natural attenuation processes, and (3) quantify a source term for use in models that may be applied to predict maximum contaminant concentrations in downstream wells. Recently, a number of new methods have been developed and subsequently applied to measure contaminant mass flux in groundwater in the field. However, none of these methods has been validated at larger than the laboratory-scale through a comparison of measured mass flux and a known flux that has been introduced into flowing groundwater. A couple of innovative flux measurement methods, the tandem circulation well (TCW) and modified integral pumping test (MIPT) methods, have recently been proposed. The TCW method can measure mass flux integrated over a large subsurface volume without extracting water. The TCW method may be implemented using two different techniques. One technique, the multi-dipole technique, is relatively simple and inexpensive, only requiring measurement of heads, while the second technique requires conducting a tracer test. The MIPT method is an easily implemented method of obtaining volume-integrated flux measurements. In the current study, flux measurements obtained using these two methods are compared with known mass fluxes in a three-dimensional, artificial aquifer. Experiments in the artificial aquifer show that the TCW multi-dipole and tracer test techniques accurately estimated flux, within 2% and 16%, respectively; although the good results obtained using the multi-dipole technique may be fortuitous. The MIPT method was not as accurate as the TCW method, underestimating flux by as much as 70%. MIPT method inaccuracies may be due to the fact that the method assumptions (two-dimensional steady groundwater flow to fully-screened wells) were not well-approximated. While fluxes measured using the MIPT method were consistently underestimated, the method's simplicity and applicability to the field may compensate for the inaccuracies that were observed in this artificial aquifer test.

The combined use of pumping and tracer test data enabled the derivation of equivalent average hydraulic conductivities (K avg) for each test in a heterogeneous channelized alluvial aquifer, whereas K values of the preferential flow paths were two orders of magnitude higher. Greater and earlier drawdown was generally observed along preferential flow lines in a pumping test, within an array of 21 wells. The study aim was to characterize hydraulic properties of a channelized aquifer system in New Zealand by combining tracer and pumping test data. Estimates were able to be made of the percentage of highly permeable channels within the profile (∼1.2%), effective porosity that reflected the maximum fraction of highly permeable channels within the aquifer (ϕ eff –pc ∼0.0038), and flows through highly permeable channels (∼98%) and the sandy gravel matrix material (∼2%). Using ϕ eff –pc, a tracer test K avg value (∼93 m/day) was estimated that was equivalent to pumping test values (∼100 m/day), but two orders of magnitude smaller than K calculated solely from transport through permeable channels (K pc ∼8,400 m/day). Derived K values of permeable and matrix material were similar to values derived from grain size distribution using the Kozeny-Carman equation.

The transport and fate of selected pesticides was determined at seven field sites located throughout New Zealand. Mixtures of pesticides and bromide (Br) were applied to plots and soil and water samples, collected at 1–3 monthly intervals over the study period, were analysed for residual pesticides and Br. The maximum depth of sampling varied from 0.92 to 2.5 m for the suction cup samplers and 0.8 to 1.0 m for the soil sampling. inverse modelling was used with three models, GLEAMS, IEACHM, and HYDRUS, to estimate Koc and half‐life values for the applied pesticides. diazinon and procymidone had much lower Koc values than the selected literature values (SLVs), indicating they will be much more mobile in New Zealand soils than would be expected from the SLVs. picloram had similar Koc values to the SlV at the Te awa and Twyford sites but was much less mobile in the allophanic horotiu soil, as was triclopyr. There was a slight effect of allophane on sorption for hexazinone, picloram, and triclopyr for...

The HYDRUS-1D mobile‐immobile water model (MIM) was used to evaluate the transport of fecal coliforms, Salmonella bacteriophage, and Br in 10 soils. At a fl ux of 5 mm h −1 , a pulse of dairy shed effl uent was applied to 30 large undisturbed lysimeters, followed by water irrigation. Soil types included clayey gley soil, clay loam, silt loam, silt loam over gravels, fi ne sandy loam, dune sand soil, pumice soil, and allophanic soil. Except for dune sand, modeling results showed lower mobile water contents and dispersivities for microbes than for Br, indicating the exclusion of microbes from smaller pores. The MIM-derived removal rates were in the order: volcanic soils > greywacke-derived silt loams > granular young sandy soils, and were the most variable in clayey gley loam and silt loam over gravels. Microbial reduction was 100% in allophanic soil, 16 to 18 log m −1 in pumice soil (where the unit log is the log 10 reduction in maximum concentration compared with the original concentration), and was lowest in clayey gley soil (0.1‐2 log m −1 ). For most of the other soils, the reduction was 2 to 3 log m −1 , except for 9 to 10 log m −1 for fecal coliforms in a fi ne sandy loam. The detachment rate was only 1% of the attachment rate, indicating irreversible attachment of microbes. Soil structure (macroporosity) appeared to play the most important role in the transport of microbes and Br, while soil lithology had the greatest infl uence on attenuation and mass exchange. The general pattern of predicted mobile water content agrees with the measured macroporosity, which is positively related to leaching vulnerability but negatively related to dispersivity.

Land disposal of treated human and animal effluent through pumice sand soils is a common practice around Rotorua, in the central North Island of New Zealand. There is increasing concern about the possibility of contamination of shallow pumice sand aquifers associated with this practice. In this study, we investigated the transport and attenuation of F-RNA bacteriophages and Escherichia coli in saturated pumice sand aquifer media using a field tracing experiment, and laboratory batch and column studies. The influence of dissolved organic carbon on microbial transport was also investigated by conditioning the 18 cm-long column with ultrafiltered sewage. The CXTFIT curve-fitting program was used to model the experimental data and to determine transport and attenuation parameters. Batch studies showed more than 90% adsorption of both microbial indicators onto pumice sand. High mass removal of microbial indicators was shown in the field (>99% for phage MS2 and E. coli at 2 m down gradient of the injection well; not detected at 6 m) and in the ‘clean sand’ column (65% for phage MS2 and 90% or E. coli). These results suggest that uncontaminated pumice is an effective sorbent capable of retaining microbial contaminants due to high surface area and porosity. However, in the column, with additional dissolved organic carbon, phages showed a progressive reduction in mass removal and retardation between experiments (93%, 75%, and 63% removal; retardation factor: 3.5, 2.5 and 1.2). This suggests that the organic matter competed with phages for the sorption sites, thus promoting phage transport. As a result, viral transport rates may be significantly greater in contaminated compared with uncontaminated pumice sand aquifers.

Intensification of dairying on irrigated pastures has led to concern over the microbial quality of shallow groundwater used for drinking purposes. The effects of intensive dairying and border-strip irrigation on the leaching of E. coli and Campylobacter to shallow groundwater were assessed over a three-year period in the Waikakahi catchment, Canterbury, New Zealand. Well selection excluded other sources of contamination so that the effect of dairying with border-strip irrigation could be assessed. Groundwater samples (135) were collected, mostly during the irrigation season, with E. coli being detected in 75% of samples. Campylobacter was identified in 16 samples (12%). A risk assessment of drinking water with these levels of Campylobacter was undertaken. A probability distribution was fitted to the observed Campylobacter data and the @RISK modeling software was used, assuming a dose response relationship for Campylobacter and consumption of 1 L/day of water. The probability of infection on any given day in the study area was estimated at 0.50% to 0.76%, giving an estimated probability of infection during the irrigation season of 60% to 75%. An epidemiological assessment of the Canterbury region comparing areas encompassing dairy within major irrigation schemes (∼55% border-strip irrigation) to two control groups was undertaken. Control group 1 (CG1) encompasses areas of dairying without major irrigation schemes, and a second larger control group (CG2) comprises the rest of the Canterbury region. Comparisons of the subject group to control groups indicated that there was a statistically significant increase in age-standardised rates of campylobacteriosis (CG1 Relative Risk (RR)=1.51 (95% CI = 1.31-1.75); CG2 RR = 1.51 (1.33–1.72)); cryptosporidiosis (CG1 RR = 2.08 (1.55–2.79); CG2 RR = 5.33 (4.12–6.90)); and salmonellosis (CG2 RR = 2.05 (1.55–2.71)).

This paper summarises findings from the Pathogen Transmission Routes Research Program, describing pathogen pathways from farm animals to water bodies and measures that can reduce or prevent this transfer. Significant faecal contamination arises through the deposition of faeces by grazing animals directly into waterways in New Zealand. Bridging of streams intersected by farm raceways is an appropriate mitigation measure to prevent direct deposition during herd crossings, whilst fencing stream banks will prevent access from pasture into waterways by cattle that are characteristically attracted to water. Riparian buffer strips not only prevent cattle access to waterways, they also entrap microbes from cattle and other animals being washed down‐slope towards the stream in surface runoff. Microbial water quality improvements can be realised by fencing stock from ephemeral streams, wetlands, seeps, and riparian paddocks that are prone to saturation. Soil type is a key factor in the transfer of faecal m...

Three microbial tracers – Escherichia coli J6-2, a somatic coliphage (OESR1) and endospores of Bacillus subtilis var. niger NCIB 8649 tracer strain JHI – were added to effluent flood irrigated onto border dyke strips at a sewage treatment plant near Christchurch, New Zealand. All three tracers, and three effluent indicators – faecal coliforms, F-RNA phages, and chloride – were recovered in a bore, approximately 100 m downstream. A simple spatial model was applied to the breakthrough curves (BTCs) in the bore, using a series of hypothetical “entry points” in the strips. This analysis indicated effluent transport velocities through the 16.8 m deep vadose zone of between 15.7 and 39.2 m hr− 1. The shapes of the BTCs for the microorganisms and chloride were very different, suggesting that they reached the groundwater table via two pathways: – both underwent rapid transport to the groundwater though macropores, but chloride also underwent far slower (matrix) transport though micropores. The BTC shapes also suggested transport velocities in the vadose zone of E. coli J6-2 > B. subtilis JH1 endospores > phage OESR1, which is consistent with the theory of pore size exclusion, based on particle size. Reductions in microbial concentrations were ≈100 times greater than for chloride, and occurred rapidly, suggesting that up to 99% of the microorganisms underwent early exclusion from macropore flow and were removed during matrix flow. Nevertheless, the results show that substantial numbers of bacteria and viruses will still reach the groundwater through macropores beneath effluent irrigation schemes located on alluvial gravel formations.

The degradation, sorption and transport of atrazine, hexazinone and procymidone in saturated coastal sand aquifer media were investigated in batch and column experiments. The pesticides were incubated with sterilised and non-sterilised groundwater or a mixture of groundwater and the aquifer material in the dark at 15°C for 120 days. The estimated half-lives of the pesticides (and their ranges) in the mixture of groundwater and aquifer sand were 36 (31–40), 54 (40–77) and 84 (46–260) days for atrazine, procymidone and hexazinone, respectively. Compared with the relevant results for the groundwater–sand mixture phase, the estimated half-life of pesticides in the groundwater phase alone was shorter for procymidone (21 days) but longer for hexazinone (134 days); atrazine was not degraded in the groundwater phase. Chemical degradation appeared to have played the predominant role in the degradation of hexazinone and procymidone in the aquifer system, while both chemical and biological processes seemed to be important for the degradation of atrazine. Batch isothermal experiments were carried out at pH 4.6–4.7 to obtain sorption coefficients under equilibrium conditions. The isothermal data of the pesticides fitted well with the non-linear Freundlich function with an exponent of sorption coefficient that was greater than one. Contrary to reports in the literature, sorption of atrazine was the greatest, and procymidone was slightly more sorbed than hexazinone. A column experiment was conducted at a typical field-flow velocity of 0.5 m day−1 over 60 days to study pesticide attenuation and transport in flow dynamic conditions. Retardation factors, R, derived from a two-site sorption/desorption model were 8.22, 1.76 and 1.63 for atrazine, procymidone and hexazinone, respectively. Atrazine displayed the lowest mobility and the mobility of procymidone was only slightly less than that of hexazinone, which is consistent with observations in the batch experiment. A possible explanation for these observations is that ionic atrazine is bound to oppositely charged ionic oxides, and ionic oxides have less effect on the sorption of the non-ionic procymidone. The significant tailing in the pesticide breakthrough curves (BTCs) in comparison with the bromide BTC, together with model-simulated results, suggests that the transport of the pesticides was under chemical non-equilibrium conditions with R values that were less than their equivalent values predicted using the batch equilibrium isothermal data. As a result of non-linear kinetic sorption, retardation factors of the pesticides in groundwater systems would not be constant and will decrease with decreasing pesticide concentrations and increasing flow velocities. Hence, the use of equilibrium isotherm data will probably over-predict the sorption of pesticides in groundwater systems. Rhodamine WT, a commonly used groundwater tracer, was significantly retarded (R = 5.48) and its BTC was much more spread out than the bromide BTC. Therefore, it would not be a good tracer for the indication of groundwater flow velocity and dispersion for the coastal sand aquifer system. In contrast to some aquifer media, the dye tracer was unsuitable as a marker of the appearance of atrazine in a coastal sand aquifer system. Copyright © 2004 Society of Chemical Industry

A total of 133 wells throughout New Zealand were sampled for the 2002 National Survey of Pesticides in Groundwater. The survey objectives were to provide a national overview of pesticides in New Zealand's groundwater systems, to examine changes with time from earlier surveys, and to examine factors linked with pesticide contamination. The samples were screened for atrazine in the laboratory using an ELISA test kit and, as a result of this screening, samples positive for atrazine were analysed for 58 different pesticides using gas chroma‐tography‐mass spectrometry (GCMS). Blind duplicate samples (6%) and quality control samples (17% of the negative ELISA screen samples) were also analysed by GCMS. Three regional councils carried out their own pesticide surveys around the same time but submitted the samples for analysis to a different laboratory. Their results are included to give a national perspective. Pesticides were detected in 28 wells (21%), with 13 wells (10%) having two or more pesticides d...

The transport and attenuation of cadmium (Cd) and rhodamine WT (RWT) in a pumice sand aquifer media was investigated using column experiments to study a scenario of point‐source contamination. A pore‐water velocity of 1.7–1.8 m/day, which is a typical field groundwater velocity in a pumice sand aquifer system, was applied to triplicate columns. A pulse of a solution containing Cd and RWT, together with the conservative tracer tri‐tiated water (3H2O) at pH = 7, was introduced into the columns. Experimental results showed that concentration breakthrough curves (BTCs) of 3H2O were symmetrical and fitted well into an equilibrium model. In contrast, BTCs of Cd and RWT were asymmetrical with significant tailings and fitted well with a two‐site adsorption/desorption model. The symmetric 3H2O BTCs suggest that physical non‐equilibrium was absent in the experimental system, therefore the asymmetrical BTCs of Cd and RWT were attributed to chemical non‐equilibrium. Modelling results showed that, in comparis...

Setback distances between septic tank systems and the shorelines of Lake Okareka, New Zealand were determined from model simulations for a worst-case scenario, using the highest hydraulic conductivity and gradient measured in the field, removal rates of the microbial indicators (Escherichia coli and F-RNA phages) determined from a column experiment, and maximum values of the design criteria for the disposal system, and assuming an absence of an unsaturated zone, a continuous discharge of the raw effluent from a failed or non-complying treatment system (both indicators at concentrations of 1×107 counts/100 ml) into the groundwater and no sorption of pathogens in the aquifer. Modelling results suggest that the minimal setback distances were 16 m to satisfy the New Zealand Recreational Water Quality Guidelines for E. coli

The primary objective of this project is to identify gaps, whether real or perceived, that hinder effective groundwater management in New Zealand. These gaps show as gaps in information, gaps in im...

In this note, we applied the temporal moment solutions of [Das and Kluitenberg, 1996. Soil Sci. Am. J. 60, 1724] for one-dimensional advective-dispersive solute transport with linear equilibrium sorption and first-order degradation for time pulse sources to analyse soil column experimental data. Unlike most other moment solutions, these solutions consider the interplay of degradation and sorption. This permits estimation of a first-order degradation rate constant using the zeroth moment of column breakthrough data, as well as estimation of the retardation factor or sorption distribution coefficient of a degrading solute using the first moment. The method of temporal moment (MOM) formulae was applied to analyse breakthrough data from a laboratory column study of atrazine, hexazinone and rhodamine WT transport in volcanic pumice sand, as well as experimental data from the literature. Transport and degradation parameters obtained using the MOM were compared to parameters obtained by fitting breakthrough data from an advective-dispersive transport model with equilibrium sorption and first-order degradation, using the nonlinear least-square curve-fitting program CXTFIT. The results derived from using the literature data were also compared with estimates reported in the literature using different equilibrium models. The good agreement suggests that the MOM could provide an additional useful means of parameter estimation for transport involving equilibrium sorption and first-order degradation. We found that the MOM fitted breakthrough curves with tailing better than curve fitting. However, the MOM analysis requires complete breakthrough curves and relatively frequent data collection to ensure the accuracy of the moments obtained from the breakthrough data.

The concentrations, solubility and mobility of Cr, Cu, Ni, Pb and Zn were measured over a four year period in soil from a site that had received over 1000 t ha-1 wet, undigested, sewage sludge (on average, 15% dry solids). The pH of this light-textured sandy soil was markedly reduced after sludge application (to ≤4 in some samples), presumably as a result of breakdown of the unstable organic matter, nitrification of the NH4 +-N and sulphide oxidation. As a consequence, soil solution concentrations of Cu, Ni, and especially, Zn were initially elevated, and this was reflected in high plant uptake of Zn and elevated levels of all three metals in some groundwater wells. An extensive liming programme resulted in soil pH values generally between 5 and 6, more normal for this soil, in the following years. Soil solution metal concentrations were substantially lower, e.g., Zn from a high of 27 mg kg-1 in 1995 to 0.04 mg kg-1 in the equivalent sample in 1999. Herbage Zn concentrations declined accordingly and overall there was a strong relationship between plant metal uptake and soil solution concentration of this element (R2 = 0.84), although not for any of the other metals. Our results suggested that, for this soil, pH was by far the greatest determinant of metal solubility and that the metal source, whether sewage sludge or geochemical, had little influence. Results from extractants that solubilise other metal phases, i.e., NaNO3, EDTA and HNO3, are also presented and discussed.

This paper investigates the effects of pore-water velocity on chemical nonequilibrium during transport of Cd, Zn, and Pb through alluvial gravel columns. Three pore-water velocities ranging from 3 to 60 m/day were applied to triplicate columns for each metal. Model results for the symmetric breakthrough curves (BTCs) of tritium (3H2O) data suggest that physical nonequilibrium components were absent in the uniformly packed columns used in these studies. As a result, values of pore-water velocity and dispersion coefficient were estimated from fitting 3H2O BTCs to an equilibrium model. The BTCs of metals display long tailing, indicating presence of chemical nonequilibrium in the system, which was further supported by the decreased metal concentrations during flow interruption. The BTCs of the metals were analysed using a two-site model, and transport parameters were derived using the CXTFIT curve-fitting program. The model results indicate that the partitioning coefficient (beta), forward rate (k1), and backward rate (k2) are positively correlated with pore-water velocity (V); while the retardation factor (R), mass transfer coefficient ((omega), and ratio of k1/k2 are inversely correlated with V. There is no apparent relationship between the fraction of exchange sites at equilibrium (f) and V. The influence of Von k2 is much greater than on R, beta, omega, and k1. A one-order-of-magnitude change in V would cause a two-order-of-magnitude change in k2 while resulting in only a one order-of-magnitude change in R, beta, omega, and k1. The forward rates for the metals are found to be two to three orders-of-magnitude greater than the corresponding backward rate. However, the difference between the two rates reduces with increasing pore-water velocity. Model results also suggest that Cd and Zn behave similarly, while Pb is much more strongly sorbed. At input concentrations of about 4 mg/l and pore-water velocities of 3-60 m/day in the groundwater within alluvial gravel, this study suggests retardation factors of 26-289 for Cd, 24-255 for Zn, and 322-6377 for Pb.

A passive sampling system for use with rhodamine WT (RWT) in groundwater tracing experiments was developed to assist in the characterisation of groundwater flow paths. Amberlite XAD-7 resin was found to be suitable for adsorption of RWT, which can then be extracted using an ethanol/water mix and analysed fluorometrically. Batch and column experiments showed that XAD-7 resin has a high RWT capacity. The adsorption was slightly dependent on pH, but was always above 75% under batch conditions. The resin had a high percentage mass recovery at flow velocities around 1.5 m/day, but this decreased with increasing flow velocities. Desorption of RWT off the resin in water is dependent on the flow velocity of water and the time after the peak RWT has passed. The mass of RWT extracted from the resin bags correlated very well with both the RWT mass flux in the water and the peak concentrations observed in the monitoring wells in a field experiment. The results of resin bags were reproducible in the field with a mean coefficient of variation equal to 16%. This method has been successfully applied to two field situations with different flow velocities to indicate groundwater flow paths.

A field tracer experiment, simulating point source contamination, was conducted to investigate attenuation and transport of atrazine, hexazinone and procymidone in a volcanic pumice sand aquifer. Preliminary laboratory incubation tests were also carried out to determine degradation rates. Field transport of the pesticides was observed to the significant under non-equilibrium conditions. Therefore, a two-region/two-site non-equilibrium transport model, N3DADE, was used for analysis of the field data. A lump reduction rate constant was used in this paper to encompass all the irreversible reduction processes (e.g. degradation, irreversible adsorption, complexation and filtration for the pesticides adsorbed into particles and colloids) which are assumed to follow a first-order rate law. Results from the field experiment suggest that (a) hexazinone was the most mobile (retardation factor R = 1.4) and underwent least mass reduction; (b) procymidone was the least mobile (R = 9.26) and underwent the greatest mass reduction; (c) the mobility of atrazine (R = 4.45) was similar to that of rhodamine WT (R = 4.10). Hence, rhodamine WT can be used to delimit the appearance of atrazine in pumice sand groundwater. Results from the incubation tests suggest that (a) hexazinone was degraded only in the mixture of groundwater and aquifer material (degradation rate constant = 4.36 x 10(-3) day-1); (b) procymidone was degraded not only in the mixture of groundwater and aquifer material (rate constant = 1.12 x 10(-2) day-1) but also in the groundwater alone (rate constant = 2.79 x 10(-2) and-1); (c) atrazine was not degraded over 57 days incubation in either the mixture of aquifer material and groundwater or the groundwater alone. Degradation rates measured in the batch tests were much lower than the total reduction rates. This suggests that not only degradation but also other irreversible processes are important in attenuating pesticides under field conditions. Hence, the use of laboratory-determined degradation rates could underestimate reduction of pesticides in field conditions.

A total of 95 wells throughout New Zealand were sampled during summer 1998/99 and analysed for a range of pesticides using gas chroma‐tography‐mass spectroscopy (GCMS). Thirty‐three wells (35%) had pesticides including triazine metabolites detected, with 18 wells (19%) having two or more pesticides detected. Only one well (K38/ 0172) had pesticides detected at levels greater than the maximum acceptable value (MAV) for drinking water. There were 20 different pesticides detected, usually at very low concentrations, as well as two triazine metabolites. Fifty‐seven out of the 75 pesticide detections (76%) belonged to the triazine group, with only five of these (9%) being >1 mg m−3 and 74% of these being 1 mg m−3 with all three detections being in Well K38/ 0172. About half (44%) of the non‐triazine pesticides were

Two 15 m×15 m field plots, a Te Awa silt loam and a Twyford fine sandy loam, located in Hawkes Bay, New Zealand, were applied with bromide, picloram, atrazine, and simazine. The Te Awa subsoil was a heterogeneous coarse sand and sandy gravel, and the Twyford subsoil was a more homogenous fine sandy loam. The underlying aquifers were composed of alluvial gravels at both sites with the water tables generally between 4–5 m below ground level. The sites were monitored for 2.2–3.5 years at approximately monthly intervals using suction cups in the unsaturated zone and monitoring wells in groundwater. HYDRUS-2D was used to simulate water movement and solute transport in soil and groundwater in a domain with a depth of 10 m and length of 68 m, including a 4.5-m unsaturated zone. The model simulated well the general trend of field observations for soil water content ( θ ) and potential ( ψ s ), and the values matched better for the soils with less heterogeneity. For the soils with significant surface cracks, the simulated θ values were overestimated. On the other hand, for the soil layer perching on top of a less permeable layer, the simulated θ values were underestimated. Simulated pesticide concentrations using the “best available literature values” (BALVs) of organic carbon distribution coefficient ( K oc ) and half-life ( T 1/2 ) were generally lower than those observed. At early times in the trails, most simulations using BALVs were still within the same order of magnitude as observed concentrations for the shallow depths. However, at greater depths and later times, there were major differences between observed and simulated concentrations. The model was then calibrated for K oc and T 1/2 values using observed data with an aid of the PEST optimisation package. Despite higher organic contents found in the topsoil, optimised K oc values for pesticides were consistently lower for the topsoil than for the subsoil, and were also lower than the BALVs except for picloram, possibly as a result of preferential flow in the topsoil. Compared to the BALVs, picloram was much more persistent but slightly more sorptive in both soil types, and atrazine and simazine were more persistent in the Te Awa soils but less persistent in the Twyford soils. The optimised K oc values for all three pesticides were generally greater, or close to, the BALVs in the subsoil of both sites. HYDRUS-2D provided a reasonably good link for pesticide transport in both the unsaturated zone and groundwater. Simulated pesticide concentrations in groundwater using optimised values were generally similar to the observed values. Both observed and simulated bromide and pesticide concentrations indicated that solutes leached more quickly through the soils that were coarser and more heterogeneous, but were more diluted in the groundwater system that was more heterogeneous, conductive, and dispersive. Significant levels of picloram were found in groundwater 22 and 53 m down-gradient of the Twyford and Te Awa plot, respectively. Both simulated and observed atrazine and simazine concentrations in groundwater were less than detection limits.

The Burwood landfill, which serves the city of Christchurch, New Zealand, is situated on coastal sands underlain by a sequence of aquifers and aquitards. Groundwater flow is toward the coast, located approximately 700 m from the landfill boundary. Shortly after completion of the first phase of the landfill, an array of wells was installed to detect any contaminant from the landfill. Leachate was detected in the wells closest to the landfill. A shallow electromagnetic (EM31) survey was carried out between the landfill and the coast, in order to delineate any leachate plume that may be present. On the basis of the geophysical results, a contaminant plume and buried channels connected to the coast were identified. Leachate flow initially occurs in what is probably a channel or pair of channels. Downgradient, the plume spreads out to the north and south as it moves eastward toward the coast. Using the geophysical results as a guide, a new set of wells was installed to confirm the presence of high leachate concentrations. Pore-water sampling confirms the presence of a leachate plume.

The relative attenuation of rhodamine WT dye, two strains of Escherichia coli, Bacillus subtilis endospores, and the F‐RNA bacteriophage MS2 in an alluvial gravel aquifer was investigated in two tracing experiments at Burnham, near Christchurch, New Zealand. A simulated concentration curve was fitted to the observed breakthrough curves using the contaminant transport model AT123D, by optimising hydraulic conductivity (K), longitudinal dispersivity (αx), and a removal constant (λ) (which includes die‐off and physical removal processes) with the Parameter Estimation (PEST) optimisation routine. When comparing the parameters, the hydraulic conductivity was converted to velocity (V). The V ranking was E. coli 2690 > B. subtilis endospores > rhodamine WT in Experiment 1 and E. coli J6–2 > phage MS2 > rhodamine WT in Experiment 2. These rankings are consistent with the concept of pore size exclusion, whereby larger particles are preferentially transported in the larger interconnected pores where water ...

A natural‐gradient tracer experiment and laboratory batch tests were conducted to study attenuation and transport of atrazine and picloram in an alluvial gravel aquifer. An analytical transport model, AT123D, was used to analyse the field data. Data analysis suggests that there was no retardation and degradation of atrazine and picloram in the aquifer over a distance of 90 m within a period of 49 h. In the batch tests with a much longer time duration (194 days), atrazine concentrations significantly decreased and picloram concentrations showed a small decrease. It is considered that the rapid decrease in atrazine levels in the first 2 days was sorption‐dominated and the slow decrease subsequently was mainly because of degradation and partially the result of slow sorption. If it is assumed that the decrease in the first 2 days was all the result of sorption and it had reached equilibrium, the estimated Kd values are 0.04 ml/g for atrazine, and 0.02 ml/g for picloram. Rates of atrazine degradation ...

The transport of Cd in alluvial gravels was investigated using batch tests and miscible displacement experiments with large and small columns. Batch tests indicates that Cd adsorption fitted the Freundlich isotherm reasonably well and was highly nonlinear. The sorption of Cd under batch conditions was essentially complete within a few minutes, followed by a time-dependent slow sorption in weeks. A large column (200 cm long, 19 cm diameter) was injected with pulse solutions containing Cd, Br, Cl, and rhodamine WT at pore–water velocities of 20 and 61 m/day; while the small column (18 cm long, 10 cm diameter) was injected with Br and Cd pulses at pore–water velocities of 18 and 58 m/day. Breakthrough curves (BTCs) of Cd were highly asymmetric while those of other solutes were essentially symmetric, suggesting the presence of a non-equilibrium component for the Cd transport. This was further evidenced by decreases in Cd concentrations when flow was interrupted. Under all conditions investigated, asymmetry in Cd BTCs essentially resulted from chemical non-equilibrium as physical non-equilibrium was not present. Both equilibrium and non-equilibrium models, as incorporated in CXTFIT, were used to describe observed BTCs of Cd. Dispersivity was obtained from the nonreactive solute Br data, and it was then held constant for the other solutes. The retardation factor (R) values were estimated based on results from batch tests and the time moment method. For comparison purposes, the R values of the Cd data were also simulated from the two-site models. The values of the partitioning coefficient (β) and the mass transfer coefficient (ω) were estimated from two-region/site models. Modelling results suggest that (1) Cd transport was mainly controlled by rate-limited sorption; (2) the scale effect on Cd transport was minor for the reasonably well sorted material investigated, with a slight increase in the degree of equilibrium in the large column. Small columns may be used to obtain fast experimental results for homogeneous medium. However, if heterogeneity and preferential flow is important, larger columns are recommended. (3) it was evidenced that the degree of chemical non-equilibrium increased with increasing pore–water velocities, however the change was not major for the flow rates investigated (18–61 m/day); and (4) equilibrium models could provide apparently good fits to skewed BTCs by overestimating dispersivity, which incorporates all the effects from the dispersion and diffusion within both mobile and immobile liquid phases and/or type-1 and type-2 sorption sites. Comparatively, non-equilibrium models described the Cd data better and provided a more correct explanation for the spreading and asymmetry of the Cd BTC.