Transport of microplastics in stormwater treatment systems under freeze-thaw cycles: Critical role of plastic density.

Stormwater treatment systems remove and accumulate microplastics from surface runoff, but some of them can be moved downward to groundwater by natural freeze-thaw cycles. Yet, it is unclear whether or how microplastic properties such as density could affect the extent to which freeze-thaw cycles would move microplastics in the subsurface. To examine the transport and redistribution of microplastics in the subsurface by freeze-thaw cycles, three types of microplastics, with density smaller than (polypropylene or PP), similar to (polystyrene or PS), or greater than (polyethylene terephthalate or PET) water, were first deposited on the top of packed sand-the most common filter media used in infiltration-based stormwater treatment systems. Then the columns were subjected to either 23 h of drying at 22 °C (control) or freeze-thaw treatment (freezing at -20 °C for 6 h and thawing at 22 °C for 17 h) followed by a wetting event. The cycle was repeated 36 times, and the effluents were analyzed for microplastics. Microplastics were observed in effluents from the columns that were contaminated with PET and subjected to freeze-thaw cycles. Comparison of the distribution of microplastics in sand columns at the end of 36 cycles confirmed that freeze-thaw cycles could disproportionally accelerate the downward mobility of denser microplastics. Using a force balance model, we show that smaller microplastics (<50 µm) can be pushed at higher velocity by the ice-water interface, irrespective of the density of microplastics. However, plastic density becomes critical when the size of microplastics is larger than 50 µm. The coupled experimental studies and theoretical framework improved the understanding of why denser microplastics such as PET and PVC may move deeper into the subsurface in the stormwater treatment systems and consequently elevate groundwater pollution risk.

Depth sequence distribution of water extractable colloidal phosphorus and its phosphorus speciation in intensively managed agricultural soils.

Legacy phosphorus (P) has accelerated the subsurface transport of colloidal P (CP) in intensively managed agricultural soils in the Midwestern U.S. Because of its high P sorption capacity and mobility, understanding the depth sequence distribution of mobile CP and its speciation in the soil profile is critical in assessing total P (TP) loss to protect the water quality of adjacent water bodies. In this study, physicochemical properties of water-extractable colloids (WECs) from the soil profile at 0-180 cm were characterized using conventional wet chemical analysis. Solution P-31 nuclear magnetic resonance spectroscopy (NMR), P and Fe K-edge X-ray absorption spectroscopy, and transmission electron microscopy were also used to understand P speciation and mineralogy of CP. Percent recovery of WECs per bulk soil increased more than three times with increasing depth. Considering mildly alkaline pH of pore water and negative zeta potential (-21 ± 4 mV) of WECs (size: 1.65 ± 0.45 µm), the transport of P rich WECs (TP: approximately 210-700 mg kg-1) were facilitated from surface to subsoils. Generally, TP in WEC decreased with increasing depth. Interestingly, WECs in subsoil contain organic P (OP) as much as 60 mg kg-1. NMR analysis clearly showed the presence of OP monoesters, OP diesters, and orthophosphate in these particles. Both orthophosphate and OP species interacted with iron oxyhydroxides, calcite, and aluminol functional groups of gibbsite and or phyllosilicates. The study showed the availability of WECs from surface to subsoils that carry orthophosphate as well as OP in legacy P impacted agricultural soils in the Midwestern U.S.

Attenuation and transport of human enteric viruses and bacteriophage MS2 in alluvial sand and gravel aquifer media-laboratory studies.

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.

High flow event induced the subsurface transport of particulate phosphorus and its speciation in agricultural tile drainage system.

Subsurface storm flow of phosphorus (P), including particulate P, has been recently discussed as an important P transport path in contrast to typical surface runoff events. However, P speciation, and P concentration during storm events has not been extensively investigated; therefore, its contribution to the water quality is not clearly understood. In this study, the physicochemical properties of particulate P in tile water samples during a high flow event were investigated in Midwestern agricultural lands using wet chemical methods, 31P Nuclear Magnetic Resonance spectroscopy and P K-edge X-ray absorptions near edge structure spectroscopy. In slightly alkaline pH tile water, total P was ranging from ∼0.06 to 0.22 mg L-1, which is significantly greater than dissolved reactive P (DRP) (∼0.02-0.08 mg L-1). The tile water contains P enriched particulate matters (∼200-660 mg L-1). Total P in the colloidal fraction was from 1013 to 2270 mg kg-1. Phosphate and organic P species, especially monoesters, are sorbed in soil colloids like calcite, and iron oxides, and colloids are effective carriers of P in the subsurface transport process during storm events. The results of this study show that storm events can accelerate the subsurface transport of P with soil particles in addition to DRP.

Porous media transport of iron nanoparticles for site remediation application: A review of lab scale column study, transport modelling and field-scale application.

Injection of surface modified zero valent iron nanoparticles for in situ remediation of soil, contaminated with an array of pollutants has attracted great attention due to the high reactivity of zero valent iron towards a broad range of contaminants, its cost effectiveness, minimal physical disruption and low toxicity. The effectiveness of this technology relies on the stability and mobility of injected iron nanoparticles. Hence the development of a modelling tool capable of predicting nZVI transport is indispensable. This review provides state of the art knowledge on the mobility of iron nanoparticles in porous media, mechanisms involved in subsurface retention of nZVI based on continuum models and field scale application. Special attention is given to the identification of the influential parameters controlling the transport potential of iron nanoparticles and the available numerical models for the simulation of laboratory scale transport data.

Fate and transport of sulfidated nano zerovalent iron (S-nZVI): A field study.

Treatment of nano zerovalent iron (nZVI) with lower valent forms of sulfur compounds (sulfidation) has the potential to increase the selectivity and reactivity of nZVI with target contaminants and to decrease inter-particle aggregation for improving its mobility. These developments help in addressing some of the long-standing challenges associated with nZVI-based remediation treatments and are of great interest for in situ applications. Herein we report results from a field-scale project conducted at a contaminated site. Sulfidated nZVI (S-nZVI) was prepared on site by first synthesizing carboxymethyl cellulose (CMC) stabilized nZVI with sodium borohydride as a reductant and then sulfidating the nZVI suspension by adding sodium dithionite. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy (EDS) of CMC-S-nZVI, from synthesis barrels, confirms the presence of both discrete spherical nZVI-like particles (∼90 nm) as well as larger irregular structures (∼500 nm) comprising of iron sulfides. This CMC-S-nZVI suspension was gravity fed into a sandy material and monitored through multiple multi-level monitoring wells. Samples collected from upstream and downstream wells suggest very good radial and vertical iron distribution. TEM-EDS analysis from the recovered well samples also indicates the presence of both nZVI-like particles as well as the larger flake-like structures, similar to those found in the injected CMC-S-nZVI suspension. This study shows that S-nZVI stabilized with CMC can be safely synthesized on site and is highly mobile and stable in the subsurface, demonstrating for the first time the field applicability of S-nZVI.

Climate change impacts the subsurface transport of atrazine and estrone originating from agricultural production activities.

Climate change will impact soil properties such as soil moisture, organic carbon and temperature and changes in these properties will influence the sorption, biodegradation and leaching of trace organic contaminants to groundwater. In this study, we conducted a modeling case study to evaluate atrazine and estrone transport in the subsurface under current and future climate conditions at a field site in central Nebraska. According to the modeling results, in the future, enhanced evapotranspiration and increased average air temperature may cause drier soil conditions, which consequently reduces the biodegradation of atrazine and estrone in the water phase. On the other hand, greater transpiration rates lead to greater root solute uptake which may decrease the concentration of atrazine and estrone in the soil profile. Another consequence of future climate is that the infiltration and leaching rates for both atrazine and estrone may be lower under future climate scenarios. Reduced infiltration of trace organic compounds may indicate that lower trace organic concentrations in groundwater may occur under future climate scenarios.

State of the art review and future directions in oil spill modeling.

A review of the state of the art in oil spill modeling, focused on the period from 2000 to present is provided. The review begins with an overview of the current structure of spill models and some lessons learned from model development and application and then provides guiding principles that govern the development of the current generation of spill models. A review of the basic structure of spill models, and new developments in specific transport and fate processes; including surface and subsurface transport, spreading, evaporation, dissolution, entrainment and oil droplet size distributions, emulsification, degradation, and sediment oil interaction are presented. The paper concludes with thoughts on future directions in the field with a primary focus on advancements in handling interactions between Lagrangian elements.

Colloid-borne forms of tetravalent actinides: a brief review.

Tetravalent actinides, An(IV), are usually assumed to be little mobile in near-neutral environmental waters because of their low solubility. However, there are certain geochemical scenarios during which mobilization of An(IV) in a colloid-borne (waterborne) form cannot be ruled out. A compilation of colloid-borne forms of tetravalent actinides described so far for laboratory experiments together with several examples of An(IV) colloids observed in field experiments and real-world scenarios are given. They are intended to be a knowledge base and a tool for those who have to interpret actinide behavior under environmental conditions. Synthetic colloids containing structural An(IV) and synthetic colloids carrying adsorbed An(IV) are considered. Their behavior is compared with the behavior of An(IV) colloids observed after the intentional or unintentional release of actinides into the environment. A list of knowledge gaps as to the behavior of An(IV) colloids is provided and items which need further research are highlighted.