Application of the re-circulating tracer well test method to determine nitrate reaction rates in shallow unconfined aquifers.

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.

Transport of Escherichia coli and F-RNA bacteriophages in a 5m column of saturated pea gravel.

The relative transport and attenuation of bacteria, bacteriophages, and bromide was determined in a 5m long x 0.3m diameter column of saturated pea gravel. The velocity (V), longitudinal dispersivity (alpha(x)) and total removal rate (lambda) were calculated from the breakthrough curves at 1m, 3m, and 5m, at a flow rate of 32Lh(-1). Inactivation (mu) rates were determined in survival chambers. Two pure culture experiments with Escherichia coli J6-2 and F-RNA phage MS2 produced an overall V ranking of E. coli J6-2>MS2>bromide, consistent with velocity enhancement, whereby larger particles progressively move into faster, central streamlines of saturated pores. Removal rates were near zero for MS2, but were higher for E. coli J6-2. In two sewage experiments, E. coli and F-RNA phage Vs were similar (but > bromide). This was attributed to phage adsorption to colloids similar in size to E. coli cells. Sewage phage removal rates were higher than for the pure MS2 cultures. The application of filtration theory suggested that, whereas free phage were unaffected by settling, this was the primary removal mechanism for the colloid-associated phage. However, cultured and sewage E. coli removal rates were similar, suggesting the dominance of free E. coli cells in the sewage. When MS2 was attached to kaolin particles, it was transported faster than free MS2, but at similar rates to sewage phage. The mu values indicated little contribution of inactivation to removal of either cultured or sewage microorganisms. The results showed the importance of association with colloids in determining the relative transport of bacteria and viruses in gravels.

Effects of pH, ionic strength, dissolved organic matter, and flow rate on the co-transport of MS2 bacteriophages with kaolinite in gravel aquifer media.

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.

Validation of two innovative methods to measure contaminant mass flux in groundwater.

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.

Use of tandem circulation wells to measure hydraulic conductivity without groundwater extraction.

Conventional methods to measure the hydraulic conductivity of an aquifer on a relatively large scale (10-100 m) require extraction of significant quantities of groundwater. This can be expensive, and otherwise problematic, when investigating a contaminated aquifer. In this study, innovative approaches that make use of tandem circulation wells to measure hydraulic conductivity are proposed. These approaches measure conductivity on a relatively large scale, but do not require extraction of groundwater. Two basic approaches for using circulation wells to measure hydraulic conductivity are presented; one approach is based upon the dipole-flow test method, while the other approach relies on a tracer test to measure the flow of water between two recirculating wells. The approaches are tested in a relatively homogeneous and isotropic artificial aquifer, where the conductivities measured by both approaches are compared to each other and to the previously measured hydraulic conductivity of the aquifer. It was shown that both approaches have the potential to accurately measure horizontal and vertical hydraulic conductivity for a relatively large subsurface volume without the need to pump groundwater to the surface. Future work is recommended to evaluate the ability of these tandem circulation wells to accurately measure hydraulic conductivity when anisotropy and heterogeneity are greater than in the artificial aquifer used for these studies.

Distance and flow effects on microsphere transport in a large gravel column.

Consumption of microbially contaminated ground water can cause adverse health effects and the processes involved in pathogen transport in aquifers need to be understood. The influences of distance, flow velocity, and colloid size on colloid transport were examined in homogenous pea-gravel media using an 8-m column and three sizes (1, 5, and 10 microm) of microspheres. Experiments were conducted at three flow rates by simultaneously injecting microspheres with a conservative tracer, bromide. Observed concentrations were simulated with CXTFIT and analyzed with filtration theory. The results demonstrate that colloid concentration is strongly log-linearly related to transport distance (as suggested by filtration theory) in coarse gravels, similar to our previous field studies. In contrast, the log-linear relationship is often reported to be invalid in fine porous media. The observed log-linear relationship is possibly because straining is negligible in the coarse gravels investigated. This has implications in predicting setback distances for land disposal of effluent, and suggests that setback distances in gravel aquifers can be estimated using constant spatial removal rates (f). There was an inverse relationship between transport distance and colloidal concentration, but not with temporal attachment rate (katt) and collision coefficient (alpha). Increases in flow velocity result in increasing colloidal recovery, katt and alpha but decreasing f. Increases in sphere size result in decreasing colloidal recovery with increasing katt, f, alpha, and velocity enhancement. Diffusion is the dominant collision mechanism for 1-microm spheres (81-88%), while settling dominates for 5- and 10-microm spheres (> 87%), and interception is very small for all spheres investigated.

Degradation and sorption of atrazine, hexazinone and procymidone in coastal sand aquifer media.

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 degrees 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.