Transport of silica encapsulated DNA microparticles in controlled instantaneous injection open channel experiments

Surface water tracing is a widely used technique to investigate in-stream mass transport including contaminant migration. Recently, a microparticle tracer was developed with unique synthetic DNA encapsulated in an environmentally-friendly silica coating (Si-DNA microparticle). Previous tracing applications of such tracers reported detection and quantification, but a massive loss of tracer mass. However, the transport behavior of these DNA-tagged microparticle tracers has not been rigorously quantified and compared with that of solute tracers. Therefore, we compared the transport behavior of Si-DNA microparticles to the behavior of solute NaCl in 6 different, environmentally representative water types using breakthrough curves (BTCs), obtained from laboratory open channel injection experiments, whereby no Si-DNA microparticle tracer mass was lost. Hereafter, we modelled the BTCs using a 1-D advection-dispersion model with one transient storage zone (OTIS) by calibrating the hydrodynamic dispersion coefficient D and a storage zone exchange rate coefficient. We concluded that the transport behavior of Si-DNA microparticles resembled that of NaCl in surface-water relevant conditions, evidenced by BTCs with a similar range of D; however, the Si-DNA microparticle had a more erratic BTC than its solute counterpart, whereby the scatter increased as a function of water quality complexity. The overall larger confidence interval of DSi-DNA was attributed to the discrete nature of colloidal particles with a certain particle size distribution and possibly minor shear-induced aggregations. This research established a solid methodological foundation for field application of Si-DNA microparticles in surface water tracing, providing insight in transport behavior of equivalent sized and mass particles in rivers.Water Resource

Effect of concentration of silica encapsulated ds-DNA colloidal microparticles on their transport through saturated porous media

We investigated the transport and retention kinetics of silica encapsulated – silica core double stranded DNA particles (SiDNASi) through 15cm saturated quartz sand columns as a function of a wide range of colloid injection concentrations (C0 = 8.7×102 - 6.6×108 particles ml-1). The breakthrough curves (BTCs) exhibited an overall 2-log increase of maximum relative effluent concentration with increasing C0. Inverse curve fitting, using HYDRUS1D, demonstrated that a 1-site first order kinetic attachment (katt) and detachment (kdet) model sufficed to explain the C0-dependent SiDNASi retention behaviour. With increasing C0, katt log-linearly decreased, which could be expressed as an overall decrease in the single-collector removal efficiency (ƞ). The decrease in ƞ was likely due to increased electrostatic repulsion between aqueous phase- solid phase colloids, formation of shadow zones downstream of deposited colloids and removal of weakly attached colloids from the solid phase (quartz sand) attributing to increased aqueous phase-solid phase intercolloidal collisions as a function of increasing SiDNASi concentration. Our results implied, firstly, that the aqueous phase colloid concentration should be carefully considered in determining colloidal retention behaviour in saturated porous media. Secondly, colloidal transport and retention dynamics in column studies should not be compared without considering colloid influent concentration. Thirdly, our results implied that the applicability of SiDNASi as a conservative subsurface tracer was restricted, since transport distance and retention was colloid concentration dependent. However, the uniqueness of the DNA sequences in SiDNASi imparts the advantage of concurrent use of multiple SiDNASi for flow tracking or porous media characterization.Water Resource

Effect of injection water ionic strength on estimating hydraulic parameters in a 3D sand tank using silica encapsulated magnetic DNA particles

We investigated the applicability of Silica encapsulated, superparamagnetic DNA particles (SiDNAmag) in determining aquifer hydraulic parameters at different ionic strengths (1 mM, 5 mM, and 20 mM phosphate buffer) of injection suspension. Thereto, in a homogeneous, unconsolidated sand tank we pulse - injected two uniquely sequenced SiDNAmag at two injection points. At 0.5 m and 0.8 m downstream from the injection points, we measured the concentration of SiDNAmags at three vertically distributed and two horizontally distributed sampling locations. We estimated the hydraulic parameter distributions from the SiDNAmag breakthrough curves through a Monte – Carlo approach and compared the parameter distributions with salt tracer breakthrough curves. Our results indicated that at all the ionic strengths, the times of peak concentrations, and the shapes of the breakthrough curves were similar to the salt tracer. As compared to the salt, a 1 – 3 log units reduction in the maximum effluent concentration of SiDNAmag was due to kinetic attachment. The attachment rate reduced from 1 mM to 5 mM phosphate buffer possibly due to competitive adsorption of phosphate onto the favourable attachment sites. SiDNAmag attachment rate further increased in 20 mM buffer suspension, possibly due to the compression of electric double layer and reduction in energy barrier for attachment. The parameter distributions of hydraulic conductivity (k), effective porosity (ne), longitudinal dispersivity (αL), vertical transverse dispersivity (αTV /αL) and horizontal transverse dispersivity (αTH /αL) estimated from the SiDNAmag and the salt tracer breakthrough curves were statistically similar. Our work contributes to the applicability of colloidal SiDNAmags for determining hydraulic parameters at different ionic strength conditions.Water Resource

Effect of channel bed sediment on the transport behaviour of superparamagnetic silica encapsulated DNA microparticles in open channel injection experiments

Recently, superparamagnetic silica encapsulated DNA microparticles (SiDNAFe) were designed and in various experiments used as a hydrological tracer. We investigated the effect of bed characteristics on the transport behaviour and especially the mass loss of SiDNAFe in open channel injection experiments. Hereto, a series of laboratory injection experiments were conducted with four channel bed conditions (no sediment, fine river sediment, coarse sand, and goethite-coated coarse sand) and two water qualities (tap water and Meuse water). Breakthrough curves (BTCs) were analysed and modelled. Mass loss of SiDNAFe was accounted for as a first-order decay process included in a 1-D advection and dispersion model with transient storage (OTIS). SiDNAFe BTCs could be adequately described by advection and dispersion with or without a first-order decay process. SiDNAFe mass recoveries exhibited a wide range, varying from 50% to 120% from sediment-free conditions to coarse (coated) sediment. In 6 out of 8 cases, SiDNAFe mass recovery was complete. Retention of SiDNAFe was 1–2 orders of magnitude greater than gravitational settling rates, as determined in Tang et al. (Hydrological Processes, e14801, 2023). We reason this was due to grain-scale hyporheic flows and coupled water-sediment-particle interactions. The dispersive behaviour of SiDNAFe generally mimicked that of NaCl tracer. We concluded that SiDNAFe can be used in tracing experiments. However, water quality and sediment characteristics may affect the fate of SiDNAFe in river environments. SiDNAFe is a promising tool for particulate multi-tracing in large rivers.Water Resource

Natural organic matter and ionic strength (CaCl₂) affect transport, retention and remobilization of silica encapsulated DNA colloids (DNAcol) in saturated sand columns

In the terrestrial environment, interactions between natural organic matter (NOM) and colloids can lead to the formation of an environmental corona around colloids, influencing their transport behaviour and, ultimately, their ecotoxicity. We used a synthetically designed colloid tagged with DNA (DNAcol) as a surrogate for natural colloids and investigated its transport in saturated sand columns. We varied the concentrations of NOM and ionic strength (CaCl2), to better understand the transport and release of DNAcol in porous media under both steady and transient porewater chemistry conditions. In addition, we aimed to understand the main factors that control deposition and release of DNAcol under tested conditions. To induce transient chemistry, we replaced the injection solution containing NOM and/or CaCl2 with Milli-Q water. The results showed that the deposition rate of DNAcol was inversely proportional to the concentration of NOM. The deposition rate increased significantly even under low ionic strength (CaCl2) conditions of tested conditions. Notably, the influence of NOM on the transport of DNAcol was most pronounced at the lowest range of [Ca2+]/DOC ratios, and the attachment of DNAcol to the sand grains was negligible. Moreover, the results showed while the DLVO theory captured the general trend of experimental results, it significantly underestimated the deposition of DNAcol in the presence of CaCl2. Under transient porewater chemistry conditions, colloid remobilization was observed upon flushing the column with Milli-Q water, leading to a secondary peak in the breakthrough curves. We observed that under transient porewater chemistry conditions, when the ionic strength of the solution was 10 mM, the magnitude of the remobilization peak was more significant compared to conditions with 1 mM ionic strength. Our work emphasized the complex interplay between water quality on the one hand and deposition and release of colloidal matter in saturated porous media on the other hand.Water Resource

Transport characteristics of DNA-tagged silica colloids as a colloidal tracer in saturated sand columns; role of solution chemistry, flow velocity, and sand grain size

In recent years, DNA-tagged silica colloids have been used as an environmental tracer. A major advantage of this technique is that the DNA-coding provides an unlimited number of unique tracers without a background concentration. However, little is known about the effects of physio-chemical subsurface properties on the transport behavior of DNA-tagged silica tracers. We are the first to explore the deposition kinetics of this new DNA-tagged silica tracer for different pore water chemistries, flow rates, and sand grain size distributions in a series of saturated sand column experiments in order to predict environmental conditions for which the DNA-tagged silica tracer can best be employed. Our results indicated that the transport of DNA-tagged silica tracer can be well described by first order kinetic attachment and detachment. Because of massive re-entrainment under transient chemistry conditions, we inferred that attachment was primarily in the secondary energy minimum. Based on calculated sticking efficiencies of the DNA-tagged silica tracer to the sand grains, we concluded that a large fraction of the DNA-tagged silica tracer colliding with the sand grain surface did also stick to that surface, when the ionic strength of the system was higher. The experimental results revealed the sensitivity of DNA-tagged silica tracer to both physical and chemical factors. This reduces its applicability as a conservative hydrological tracer for studying subsurface flow paths. Based on our experiments, the DNA-tagged silica tracer is best applicable for studying flow routes and travel times in coarse grained aquifers, with a relatively high flow rate. DNA-tagged silica tracers may also be applied for simulating the transport of engineered or biological colloidal pollution, such as microplastics and pathogens.Water Resource

Settling of superparamagnetic silica encapsulated DNA microparticles in river water

Particle tracers are sometimes used to track sources and sinks of riverine particulate and contaminant transport. A potentially new particle tracer is ~200 nm sized superparamagnetic silica encapsulated DNA (SiDNAFe). The main objective of this research was to understand and quantify the settling and aggregation behaviour of SiDNAFe in river waters based on laboratory settling experiments. Our results indicated, that in quiescent conditions, more than 60% of SiDNAFe settled within 30 h, starting with a rapid settling phase followed by an exponential-like slow settling phase in the three river waters we used (Meuse, Merkske, and Strijbeek) plus MilliQ water. In suspensions of 1000× higher particle concentrations, the hydrodynamic diameter (Dh-DLS) of SiDNAFe increased over time, with its polydispersity index (PDI) positively correlated with particle size. From these observations, we inferred that the rapid SiDNAFe settling was mainly due to homo-aggregation and not due to hetero-aggregation (e.g., with particulate matter present in river water). Incorporating a first-order mass loss term which mimics the exponential phase of the settling in quiescent conditions seems to be an adequate step forward when modelling the transport of SiDNAFe in river injection experiments. Furthermore, we validated the applicability of magnetic separation and up-concentration of SiDNAFe in real river waters, which is an important advantage for carrying out field-scale SiDNAFe tracing experiments.Water ResourcesEnvironmental Fluid Mechanic

Hydrogeology of an urban weathered basement aquifer in Kampala, Uganda

Weathered basement aquifers are vital sources of drinking water in Africa. In order to better understand their role in the urban water balance, in a weathered basement aquifer in Kampala, Uganda, this study installed a transect of monitoring piezometers, carried out spring flow and high-frequency groundwater level monitoring, slug tests and hydrochemical analyses, including stable isotopes and groundwater residence time indicators. Findings showed a typical weathered basement aquifer with a 20–50-m thickness. Groundwater recharge was 3–50 mm/year, occurring during sustained rainfall. Recharge to a deep groundwater system within the saprock was slow and prolonged, while recharge to the springs on the valley slopes was quick and episodic, responding rapidly to precipitation. Springs discharged shallow groundwater, mixed with wastewater infiltrating from onsite sanitation practices and contributions from the deeper aquifer and were characterised by low flow rates (< 0.001 m3/s), low pH (<5), high nitrate values (61–190 mg/L as NO3), and residence times of <30 years. The deeper groundwater system occurred in the saprolite/saprock, had low transmissivity (< 1 × 10−5 m2/s), lower nitrate values (<20 mg/L as NO3), pH 6–6.5 and longer residence times (40–60 years). Confined groundwater conditions in the valleys were created by the presence of clay-rich alluvium and gave rise to artesian conditions where groundwater had lower nitrate concentrations. The findings provide new insights into weathered basement aquifers in the urban tropics and show that small-scale abstractions are more sustainable in the deeper groundwater system in the valleys, where confined conditions are present.Water Resource