Evaluation of historical data on persistent organic pollutants and heavy metals in Lake Baikal: Implications for accumulation in marine environments.

Lake Baikal, the largest freshwater lake by volume, provides drinking water and aquatic food supplies to over 2.5 million people. However, the lake has been contaminated with recalcitrant pollutants released from surrounding industrial complexes, agriculture, and natural lands, thereby increasing the risk of their bioaccumulation in fish and seals. Yet, a collective analysis of historical concentration data and their bioaccumulation potential as well as what factors drive their accumulation in fish or seals remains largely unknown. We analyzed concentration data from 42 studies collected between 1985 and 2019 in water, sediment, fish, and seals of Lake Baikal. Heavy metals had the highest concentrations in water and biota followed closely by polycyclic aromatic hydrocarbons (PAHs) and organochlorines. Among organochlorines, polychlorinated biphenyls (PCBs) showed the highest levels in water, surpassing hexachlorocyclohexane (HCH) concentrations, particularly after normalizing to solubility. While naphthalene and phenanthrene exhibited the highest average concentrations among polycyclic aromatic hydrocarbons (PAHs), their relative concentrations significantly decreased upon solubility normalization. The analysis confirmed that bioconcentration and biomagnification of organochlorine pesticides, PCBs, PAHs, and heavy metals depend primarily on source strength to drive their concentration in water and secondarily on their chemical characteristics as evidenced by the higher concentrations of low-solubility PCBs and high molecular weight PAHs in water and sediment. The differential biomagnification patterns of Cu, Hg, and Zn compared to Pb are attributed to their distinct sources and bioavailability, with Cu, Hg, and Zn showing more pronounced biomagnification due to prolonged industrial release, in contrast to the declining Pb levels. Dibenzo-p-dioxins were detected in sediment and seals, but not in water or fish compartments. These data highlight the importance of addressing even low concentrations of organic and inorganic pollutants and the need for more consistent and frequent monitoring to ensure the future usability of this and other similar essential natural resources.

Natural aging of expanded shale, clay, and slate (ESCS) amendment with heavy metals in stormwater increases its antibacterial properties: Implications on biofilter design.

Aging is often expected to decrease the pathogen removal capacity of media because of exhaustion of attachment sites by adsorption of co-contaminants and dissolved organics. In contrast, the adsorption of metals naturally present in stormwater during aging could have a positive impact on pathogen removal. To examine the effect of adsorbed metals on pathogen removal, biofilter media amended with expanded clay, shale, and slate (ESCS) aggregates, a lightweight aggregate, were exposed to metals by intermittently injecting natural stormwater spiked with Cu, Pb, and Zn, and the capacity of aged and unaged media to remove Escherichia coli (E. coli), a pathogen indicator, were compared. Metal adsorption on ESCS media decreased their net negative surface charge and altered the surface properties as confirmed by zeta potential measurement and Fourier-Transform Infrared Spectroscopy (FTIR) analysis. These changes increased the E. coli adsorption capacity of aged media compared with unaged media and decreased overall remobilization of attached E. coli during intermittent infiltration of stormwater. A live-dead analysis confirmed that the adsorbed metals inactivated attached E. coli, thereby replenishing the adsorption capacity. Overall, the results confirmed that natural aging of biofilter media with adsorbed metals could indeed have a net positive effect on E. coli removal in biofilters and therefore should be included in the conceptual model predicting long-term removal of pathogens from stormwater containing mixed pollutants.

Enhanced removal of per- and polyfluoroalkyl substances in complex matrices by polyDADMAC-coated regenerable granular activated carbon.

Granular activated carbon (GAC) has been used to remove per- and polyfluoroalkyl substances (PFASs) from industrial or AFFF-impacted waters, but its effectiveness can be low because adsorption of short-chained PFASs is ineffective and its sites are exhausted rapidly by co-contaminants. To increase adsorption of anionic PFASs on GAC by electrostatic attractions, we modified GAC's surface with the cationic polymer poly diallyldimethylammonium chloride (polyDADMAC) and tested its capacity in complex water matrices containing dissolved salts and humic acid. Amending with concentrations of polyDADMAC as low as 0.00025% enhanced GAC's adsorption capacity for PFASs, even in the presence of competing ions. This suggests that electrostatic interactions with polyDADMAC's quaternary ammonium functional groups helped bind organic and inorganic ions as well as the headgroup of short-chain PFASs, allowing more overall PFAS removal by GAC. Evaluating the effect of polymer dose is important because excessive addition can block pores and reduce overall PFAS removal rather than increase it. To decrease the waste associated with this adsorption strategy by making the adsorbent viable for more than one saturation cycle, a regeneration method is proposed which uses low-power ultrasound to enhance the desorption of PFASs from the polyDADMAC-GAC with minimum disruption to the adsorbent's structure. Re-modification with the polymer after sonication resulted in a negligible decrease in the sorbent's capacity over four saturation rounds. These results support consideration of polyDADMAC-modified GAC as an effective regenerable adsorbent for ex-situ concentration step of both short and long-chain PFASs from real waters with high concentrations of competing ions and low PFAS loads.

Perfluoroalkyl acids on suspended particles: Significant transport pathways in surface runoff, surface waters, and subsurface soils.

Eroded particles from the source zone could transport a high concentration of perfluoroalkyl acids (PFAAs) to sediments and water bodies. Yet, the contribution of suspended particles has not been systematically reviewed. Analyzing reported studies, we quantitatively demonstrate that suspended particles in surface water can contain significantly higher concentrations of PFAAs than the sediment below, indicating the source of suspended particles are not the sediment but particles eroded and carried from the source zone upstream. The affinity of PFAAs to particles depends on the particle composition, including organic carbon fraction and iron or aluminum oxide content. In soils, most PFAAs are retained within the top 5 m below the ground surface. The distribution of PFAAs in the subsurface varies based on site properties and local weather conditions. The depth corresponding to the maximum concentration of PFAA in soil decreases with an increase in soil organic carbon or rainfall amount received in the catchment areas. We attribute a greater accumulation of PFAAs near the upper layer of the subsurface to an increase in the accumulation of particles eroded from source zones upstream receiving heavy rainfall. Precursor transformation in the aerobic zone is significantly higher than in the anaerobic zone, thereby making the aerobic subsurface zone serve as a long-term source of groundwater pollution. Collectively, these results suggest that suspended particles, often an overlooked vector for PFAAs, can be a dominant pathway for the transport of PFAAs in environments.

Release of soil colloids during flow interruption increases the pore-water PFAS concentration in saturated soil.

Groundwater flow through aquifer soils or packed bed systems can fluctuate for various reasons, which could affect the concentration of natural colloids and per- and polyfluoroalkyl substances (PFAS) in the pore water. In such cases, PFAS concentration could either decrease due to matrix diffusion of PFAS or increase by the detachment of colloids carrying PFAS. Yet, the effect of flow fluctuation on PFAS transport or release in porous media has not been examined. To examine the relative importance of either process, we interrupted the flow during an injection of groundwater spiked with perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), and bromide as conservative tracer through clay-rich soil, so that diffusive transport would be prominent during flow interruption. After flow interruption, the PFAS concentration did not decrease indicating an insignificant contribution of matrix diffusion. The concentration increased, potentially due to enhanced release of colloid-associated PFAS. Analysis of samples before and after flow interruption by particle size analysis and SEM confirmed an increase in soil colloid concentration after the flow interruption. XRD analysis of soil and the colloids proved that PFAS were associated with specific sites of the colloids. Due to a higher affinity of PFOA to soil colloids, the total PFOA concentration in the effluent samples increased more than PFBA after the flow interruption process. The results indicate that colloids may have a disproportionally higher role in the transport of PFAS in conditions that release colloids from porous media. Thus, fluctuations in groundwater flow can increase this colloid facilitated mobility of PFAS.

Iron amendments minimize the first-flush release of pathogens from stormwater biofilters.

First flush or the first pore volume of effluent eluted from biofilters at the start of rainfall contributes to most pollution downstream because it typically contains a high concentration of bacterial pathogens. Thus, it is critical to evaluate designs that could minimize the release of bacteria during a period of high risk. In this study, we test the hypothesis of whether an addition of iron-based media to biofilter could limit the leaching of Escherichia coli (E. coli), a pathogen indicator, during the first flush. We applied E. coli-contaminated stormwater intermittently in columns packed with a mixture of sand and compost (70:30 by volume, respectively) and iron filings at three concentrations: 0% (control), 3%, and 10% by weight. Columns packed with a mixture of sand and iron (3% or 10%) without compost were used to examine the maximum capacity of iron to remove E. coli. In columns with iron, particularly 10% by weight, the leaching of E. coli during the first flush was 32% lower than the leaching from compost columns, indicating that the addition of iron amendments could decrease first-flush leaching of E. coli. We attribute this result to the ability of iron to increase adsorption and decrease growth during antecedent drying periods. Although the addition of iron filings increased E. coli removal, the presence of compost decreased the adsorption capacity: exposure of 1 g of iron filings to 1 mg of DOC reduces E. coli removal by 8%. The result was attributed to the alteration of the surface charge of iron and blocking of adsorption sites shared by E. coli and DOC. Collectively, these results indicate that the addition of sufficient amounts of iron media could decrease pathogen leaching in the first flush effluent and increase the overall biofilter performance and protect downstream water quality.

Managed aquifer recharge implementation criteria to achieve water sustainability.

Depletion of groundwater is accelerated due to an increase in water demand for applications in urbanized areas, agriculture sectors, and energy extraction, and dwindling surface water during changing climate. Managed aquifer recharge (MAR) is one of the several methods that can help achieve long-term water sustainability by increasing the natural recharge of groundwater reservoirs with water from non-traditional supplies such as excess surface water, stormwater, and treated wastewater. Despite the multiple benefits of MAR, the wide-scale implementation of MAR is lacking, partly because of challenges to select the location for MAR implementation and identify the MAR type based on site conditions and needs. In this review, we provide an overview of MAR types with a basic framework to select and implement specific MAR at a site based on water availability and quality, land use, source type, soil, and aquifer properties. Our analysis of 1127 MAR projects shows that MAR has been predominantly implemented in sites with sandy clay loam soil (soil group C) and with access to river water for recharge. Spatial analysis reveals that many regions with depleting water storage have opportunities to implement MAR projects. Analyzing data from 34 studies where stormwater was used for recharge, we show that MAR can remove dissolved organic carbon, most metals, E. coli but not efficient at removing most trace organics, and enterococci. Removal efficiency depends on the type of MAR. In the end, we highlight potential challenges for implementing MAR at a site and additional benefits such as minimizing land subsidence, flood risk, augmenting low dry-season flow, and minimizing salt-water intrusion. These results could help identify locations in the water-stressed regions to implement specific MAR for water sustainability.

Compaction conditions affect the capacity of biochar-amended sand filters to treat road runoff.

Amending roadside soil with adsorbents such as biochar can help remove pollutants from road runoff. To maintain soil stability, the roadside soil requires compaction. However, it is unknown how compaction conditions affect the capacity of biochar-augmented roadside biofilters to infiltrate stormwater and remove pollutants. This work examines the effect of compaction conditions on the release of biochar particles disintegrated during compaction, and the change in their capacity to infiltrate stormwater and remove E. coli. The net loss of biochar particles by mobilization with stormwater was insignificant compared to the biochar remained in the filters. The initial release of biochar particles in wet-compacted biochar columns was greater than that in dry-compacted biochar. The results revealed that compaction can affect the release of biochar particles in a series of three-step processes: generation of particles by disintegration of large biochar under compaction, diffusion of particles deposited near grain walls to bulk pore water, and transport and retention of particles in constricted pore paths based on pore water connectivity. Under similar conditions, compost columns released more particles than biochar columns, suggesting biochar is more stable than compost under compaction. E. coli removal in wet-compacted columns was greater than removal in dry-compacted columns, owing to greater pore path connectivity in wet-compacted columns. These results indicate that addition of moisture during compaction can increase contaminant removal, initial particle release, and infiltration capacity of biochar-augmented sand filters for road runoff treatment. The results would help develop design guidelines for roadside stormwater treatment systems that require compaction of filter media.