Spatial, temporal, and biological factors influencing plant responses to deicing salt in roadside bioinfiltration basins.

Plants are arguably the most visible components of stormwater bioretention basins and play key roles in stabilizing soils and removing water through transpiration. In regions with cold winters, bioretention basins along roadways can receive considerable quantities of deicing salt, much of which migrates out of the systems prior to the onset of plant growth but the rest remains in the soil. The resulting effects on plants presumably vary with time (due to annual weather patterns), space (because stormwater exposure is location-dependent), and biology (because plant taxa differ in their salt tolerance). The goal of this study was to investigate the magnitude of deicing salt's effects on bioretention plants and how it varies with spatial, temporal, and biological factors. The study took place in a set of five bioretention basins in Philadelphia, USA that receive runoff from a major highway. Over a five-year period, the electrical conductivity (EC) of influent stormwater frequently exceeded 1 mS cm-1 in winter, and occasionally surpassed that of seawater (∼50 mS cm-1). In both of the years when soil EC was measured as well, it remained elevated through all spring months, especially near basin inlets and centers. Mortality of nine plant taxa ranged widely after three years (0-90%), with rankings largely corresponding to salt tolerances. Moreover, leaf areas and/or crown volumes were strongly reduced in proportion to stormwater exposure in seven of these taxa. In the three taxa evaluated for tissue concentrations of 14 potentially toxic elements (Hemerocallis 'Happy Returns', Iris 'Caesar's Brother', and Cornus sericea 'Cardinal'), only sodium consistently exceeded the toxicity limit for salt intolerant plants (500 mg kg-1). However, exceedance of the sodium toxicity limit was associated with plants' topographic positions, with median concentrations greatest in the bottom of basins and least on basin rims. This study demonstrates that deicing salts can have detrimental effects on plants in bioretention basins, with the strongest effects likely to occur in years with the greatest snowfall (and therefore deicing salt use), in portions of basins with greatest stormwater exposure (typically around inlets and centers), and in plants with minimal salinity tolerance. Our results therefore underscore the value of installing salt-tolerant taxa in basins likely to experience any frequency of deicing salt exposure.

Sonochemical degradation of PFAS in ion exchange regeneration wastes.

One of the primary technologies currently being deployed for the removal of per- and polyfluoroalkyl substances (PFAS) from water is ion exchange (IX). For regenerable IX resins, concentrated PFAS in the resulting spent brine and/or still bottoms requires further treatment. This research demonstrated that PFAS in spent brine and still bottoms can be effectively degraded sonochemically at 1000 kHz. Overall, PFAS degradation was negatively impacted by high total organic carbon (TOC) and residual methanol (MeOH) solvent (up to 50 g/kg; 5% w:w), but was enhanced by the high chloride. The addition of caustic (up to 1 N NaOH) partially mitigated the inhibition by TOC and MeOH. Sonochemical degradation of individual PFAS compounds resulted in significant mineralization to form inorganic fluoride, but small quantities of volatile organic fluorine species (VOF) were noted. This is believed to be the first report of sonochemical degradation of PFAS in ion exchange regeneration wastes, and indicates the possibility for the application of this technology as part of a complete PFAS capture and destruction treatment train.

Effects of dissolved organic carbon on potentially toxic element desorption in stormwater bioretention systems.

Stormwater runoff contains dissolved organic carbon (DOC) and potentially toxic elements (PTEs). Interactions between DOC and PTEs can impact PTE speciation and mobility, but are not fully understood. Soil samples were collected from a vegetated bioretention bed to investigate the effects of DOC (0, 15, and 50 mg-C/L) on the desorption of 10 PTEs captured by the soil media: Mn, Fe, Co, Cu, Zn, As, Cd, Sn, Sb, and Pb. In the absence of DOC, the desorbed PTE concentration from bioretention media into the aqueous phase ranking was as follows: Fe > Mn âˆ¼ Zn > Cu > Pb > Sb > As > Co > Sn âˆ¼ Cd. Increased DOC concentrations resulted in a reduction of the soil-water distribution coefficient (Kd) values. The greatest shift in Kd was observed for Cu and lowest for Sb. The PTE sorption capacities were lower for surficial soil samples (lower Kd) compared to the deep soil samples. Overall, the desorbed PTE (average midchannel 55.7 µg/g) fraction accounted for <1.1 % of the total extracted PTEs (5364 µg/g), and while this is a small percentage of the total, this is the fraction that is mobile. The extracted PTE fractions revealed that DOC reduced the organic matter-bound and carbonate-bound fractions. The PTE desorption trends suggest that reducing DOC in stormwater runoff could be an effective measure to mitigate the release of PTEs into the environment.

A modified QuEChERS sample processing method for the determination of per- and polyfluoroalkyl substances (PFAS) in environmental biological matrices.

QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample processing methods have previously been applied to a range of compounds and matrices. This study presents a modified QuEChERS sample processing method that was validated and employed for 24 per- and polyfluoroalkyl substances (PFAS) for various biological matrices. PFAS are a group of synthetic chemicals that have attracted substantial attention as some compounds are acknowledged to be persistent, toxic, and bioaccumulative. It is crucial to determine PFAS in diverse environmental matrices. Currently, limited sample processing methods for PFAS in biological matrices are available and the majority only focus on a few compounds such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Thus, there is a demand to develop a sample processing method which is effective for many commonly tested PFAS compounds in environmental biological samples. In this study, the detailed sample processing procedures and method performance are described. The highlights of this method are: •The extraction solvent and salts were adjusted for PFAS extraction from environmental biological matrices.•The modified QuEChERS method is effective for extraction and cleanup from a variety of matrices including algae, plants, invertebrates, amphibians, and fish.

Impacts of divalent cations (Mg2+ and Ca2+) on PFAS bioaccumulation in freshwater macroinvertebrates representing different foraging modes.

Per- and polyfluoroalkyl substances (PFAS) have extensively contaminated freshwater aquatic ecosystems where they can be transported in water and partition to sediment and biota. In this paper, three freshwater benthic macroinvertebrates with different foraging modes were exposed to environmentally relevant concentrations of eight perfluoroalkyl carboxylates (PFCA), three perfluoroalkyl sulfonates (PFSA), and three fluorotelomer sulfonates (FTS) at varying divalent cation concentrations of magnesium (Mg2+) and calcium (Ca2+). Divalent cations can impact PFAS partitioning to solids, especially to sediments, at higher concentrations. Sediment dwelling worms (Lumbriculus variegatus), epibenthic grazing snails (Physella acuta), and sediment-dwelling filter-feeding bivalves (Elliptio complanata) were selected due to their unique foraging modes. Microcosms were composed of synthetic sediment, culture water, macroinvertebrates, and PFAS and consisted of a 28-day exposure period. L. variegatus had significantly higher PFAS bioaccumulation than P. acuta and E. complanata, likely due to higher levels of interactions with and ingestion of the contaminated sediment. "High Mg2+" (7.5 mM Mg2+) and "High Ca2+" (7.5 mM Ca2+) conditions generally had statistically higher bioaccumulation factors (BAF) than the "Reference Condition" (0.2 mM Ca2+ and 0.2 mM Mg2+) for PFAS with perfluorinated chain lengths greater than eight carbons. Long-chain PFAS dominated the PFAS profiles of the macroinvertebrates for all groups of compounds studied (PFCA, PFSA, and FTS). These results indicate that the study organism has the greatest impact on bioaccumulation, although divalent cation concentration had observable impacts between organisms depending on the environmental conditions. Elevated cation concentrations in the microcosms led to significantly greater bioaccumulation in the test organisms compared to the experimental reference conditions for long-chain PFAS.

In situ monitoring of internal water storage reveals nitrogen first flush phenomena, intermittent denitrification, and seasonal ammonium flushing.

Internal water storage (IWS) can be included in bioretention practices to increase storage capacity or promote denitrification-the microbial reduction of nitrate to nitrogen gas. IWS and nitrate dynamics are well studied in laboratory systems. However, the investigation of field environments, consideration of multiple nitrogen species, and determination between mixing versus denitrification is lacking. This study employs in situ monitoring (∼24 h duration) of water level, dissolved oxygen (DO), conductivity, nitrogen species, and dual isotopes of a field bioretention IWS system for nine storms events over a year period. Rapid peaks in IWS conductivity, DO, and total nitrogen (TN) concentrations occurred along the rising limb of the IWS water level and indicated a first flush effect. TN concentrations generally peaked during the first ∼0.33 h of sampling and the average peak IWS TN concentration (Cmax = 4.82 ± 2.46 mg-N/L) was 38% and 64% greater than the average TN along the IWS rising and falling limb, respectively. Dissolved organic nitrogen (DON) and nitrate plus nitrite (NOx) were the dominant nitrogen species of IWS samples. However, average IWS peak ammonium (NH4+) concentrations August through November (0.28 ± 0.47 mg-N/L) demonstrated statistically significant shifts compared to February through May (2.72 ± 0.95 mg-N/L). Average lysimeter conductivity measurements were more than ten times higher February through May. The sustained presence of sodium observed in lysimeters, from road salt application, contributed to NH4+ flushing from the unsaturated media layer. Dual isotope analysis showed denitrification occurred for discrete time intervals along the tail of the NOx concentration profile and the hydrologic falling limb. Longer antecedent dry periods (17 days) did not correlate to enhanced denitrification but did correspond to more leaching of soil organic nitrogen. Results from field monitoring highlight the complexities of nitrogen management in bioretention systems. First flush behavior into the IWS suggests management to prevent TN export is most critical during the onset of a storm.

Spatial and temporal variability of per- and polyfluoroalkyl substances (PFAS) in environmental media of a small pond: Toward an improved understanding of PFAS bioaccumulation in fish.

Per- and polyfluoroalkyl substances (PFAS) are highly fluorinated compounds with many industrial applications, for instance as ingredients in fire-suppressing aqueous film-forming foams (AFFF). Several PFAS have been demonstrated to be persistent, bioaccumulative and toxic. This study better characterizes the bioaccumulation of PFAS in freshwater fish through a spatial and temporal analysis of surface water and sediment from a stormwater pond in a former Naval air station (NAS) with historic AFFF use. We sampled environmental media from four locations twice per week for five weeks and sampled fish at the end of the sampling effort. The primary PFAS identified in surface water, sediment, and biota were perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) followed by perfluorooctanoic acid (PFOA) in environmental media and perfluoroheptane sulfonate (PFHpS) in biota. We observed significant temporal variability in surface water concentrations at the pond headwaters following stochastic events such as heavy rainfall for many compounds, particularly PFHxS. Sediment concentrations varied most across sampling locations. In fish, liver tissue presented the highest concentrations for all compounds except PFHxS, which was highest in muscle tissue, suggesting the influence of fine-scale aqueous PFAS fluctuations on tissue distribution. Calculated log bioaccumulation factors (BAFs) ranged from 0.13 to 2.30 for perfluoroalkyl carboxylates (PFCA) and 0.29-4.05 for perfluoroalkane sulfonates (PFSA) and fluctuated greatly with aqueous concentrations. The variability of PFAS concentrations in environmental media necessitates more frequent sampling efforts in field-based studies to better characterize PFAS contamination in aquatic ecosystems as well as exercising caution when considering single time-point BAFs due to uncertainty of system dynamics.

Influence of microbial weathering on the partitioning of per- and polyfluoroalkyl substances (PFAS) in biosolids.

Per- and polyfluoroalkyl substances (PFAS) are a large group of man-made fluorinated organic chemicals that can accumulate in the environment. In water resource recovery facilities (WRRFs), some commonly detected PFAS tend to partition to and concentrate in biosolids where they can act as a source to ecological receptors and may leach to groundwater when land-applied. Although biosolids undergo some stabilization to reduce pathogens before land application, they still contain many microorganisms, contributing to the eventual decomposition of different components of the biosolids. This work demonstrates ways in which microbial weathering can influence biosolids decomposition, degrade PFAS, and impact PFAS partitioning in small-scale, controlled laboratory experiments. In the microbial weathering experiments, compound-specific PFAS biosolids-water partitioning coefficients (Kd) were demonstrated to decrease, on average, 0.4 logs over the course of the 91 day study, with the most rapid changes occurring during the first 10 days. Additionally, the highest rates of lipid, protein, and organic matter removal occurred during the same time. Among the evaluated independent variables, statistical analyses demonstrated that the most significant solids characteristics that impacted PFAS partitioning were organic matter, proteins, lipids, and molecular weight of organics. A multiple linear regression model was built to predict PFAS partitioning behavior in biosolids based on solid characteristics of the biosolids and PFAS characteristics with a R2 value of 0.7391 when plotting predicted and measured log Kd. The findings from this work reveal that microbial weathering can play a significant role in the eventual fate and transport of PFAS and their precursors from biosolids.

Bioaccumulation of per- and polyfluoroalkyl substances by freshwater benthic macroinvertebrates: Impact of species and sediment organic carbon content.

Per- and polyfluoroalkyl substances (PFAS) in aquatic environments have caused global concern due to their persistence, toxicity, and potential bioaccumulation of some compounds. As an important compartment of the aquatic ecosystem, sediment properties impact PFAS partitioning between aqueous and solid phases, but little is known about the influence of sediment organic carbon content on PFAS bioaccumulation in benthic organisms. In this study, three freshwater benthic macroinvertebrates - worms (Lumbriculus variegatus), mussels (Elliptio complanata) and snails (Physella acuta) - were exposed for 28 days to PFAS spiked synthetic sediment equilibrated with a synthetic surface water. Using microcosms, sediment organic carbon content - 2%, 5% and 8% - was manipulated to assess its impact on PFAS bioaccumulation. Worms were found to have substantially greater PFAS bioaccumulation compared to mussels and snails. The bioaccumulation factors (BAFs) and biota sediment accumulation factors (BSAFs) in worms were both one to two magnitudes higher than in mussels and snails, likely due to different habitat-specific uptake pathways and elimination capacities among species. In these experiments, increasing sediment organic carbon content decreased the bioaccumulation of PFAS to benthic macroinvertebrates. In worms, sediment organic carbon content was hypothesized to impact PFAS bioaccumulation by affecting PFAS partitioning and sediment ingestion rate. Notably, the BSAF values of 8:2 fluorotelomer sulfonic acid (FTS) were the largest among 14 PFAS for all species, suggesting that the benthic macroinvertebrates probably have different metabolic mechanisms for fluorotelomer sulfonic acids compared to fish evaluated in published literature. Understanding the impact of species and sediment organic carbon on PFAS bioaccumulation is key to developing environmental quality guidelines and evaluating potential ecological risks to higher trophic level species.

Bioretention soil capacity for removing nutrients, metals, and polycyclic aromatic hydrocarbons; roles of co-contaminants, pH, salinity and dissolved organic carbon.

Conventional bioretention soil media (BSM: e.g., loamy sand) is employed in infiltration-based stormwater management practices, but concerns exist on its limited sorption capacity. However, limited quantitative data is available, particularly considering the wide range of contaminants and water quality conditions that occur in stormwater. This study utilized batch tests to investigate the capability of conventional BSM for simultaneous removal of three nutrients (ammonium, nitrate, and phosphate), six metals (Cd, Cr, Cu, Ni, Pb and Zn), and four polycyclic aromatic hydrocarbons (PAHs: naphthalene, acenaphthylene, phenanthrene, and pyrene) from synthetic stormwater. Moreover, the effects of co-contaminants and different stormwater chemistry parameters (pH, salinity, and dissolved organic carbon (DOC)) on BSM sorption capacity were investigated. BSM was not effective for nutrients removal; however, it had good removal efficiency for metals such as Cu, Pb, and Cr which are less soluble at neutral pH values compared to metals such as Ni, Cd and Zn. Moreover, BSM was effective for removing PAHs with higher hydrophobicity such as pyrene and phenanthrene. Metals sorption capacity of BSM was greater at higher pH, lower salinity and DOC; however, the sorption capacity of BSM for PAHs was not sensitive to stormwater chemistry parameters. However, competitive sorption had a notable effect on low molecular weight PAHs, Cd, and Ni. This study provides a quantitative evaluation of the BSM performance and compares the sorption capacity to potential sorptive amendments used in stormwater management. While select sorbent amendments out-performed the BSM, this was not universal and was contaminant specific; careful consideration of water quality enhancement goals and solution chemistry are required in selecting a sorbent. Overall, this study identifies the possible limitations in BSM compositions and factors that may adversely affect BSM sorption capacity, and finally describes options to enhance BSM performance and recommendations for future research.

Exposure pathways and bioaccumulation of per- and polyfluoroalkyl substances in freshwater aquatic ecosystems: Key considerations.

Due to the bioaccumulative behavior, toxicity, and recalcitrance to degradation, per- and polyfluoroalkyl substances (PFAS) are a focus for many researchers investigating freshwater aquatic ecosystems. PFAS are a diverse set of chemicals that accumulate and transport quite differently in the environment depending on the length of their fluoroalkyl chains and their functional groups. This diversity in PFAS chemical characteristics combined with varying environmental factors also impact the bioaccumulation of these compounds in different organisms. In this review, we evaluate environmental factors (such as organic carbon, proteins, lipids, and dissolved cations) as well as PFAS characteristics (head group, chain-length, and concentration) that contribute to the significant variation seen in the literature of bioaccumulation metrics reported for organisms in aquatic ecosystems. Of the factors evaluated, it was found that PFAS concentration, dissolved organic matter, sediment organic matter, and biotransformation of precursor PFAS tended to significantly impact reported bioaccumulation metrics the most. Based on this review, it is highly suggested that future studies provide sufficient details of important environmental factors, specific organism traits/ behavior, and PFAS concentrations/compounds when reporting on bioaccumulation metrics to further fill data gaps and improve our understanding of PFAS in aquatic ecosystems.

The impact of bioretention column internal water storage underdrain height on denitrification under continuous and transient flow.

Internal water storage (IWS), a below-grade saturated layer, is a bioretention design component created by adjusting the underdrain outlet elevation. Anaerobic conditions and the presence of a carbon source in IWS facilitates denitrification. Yet it remains unclear how underdrain height within the IWS impacts nitrate (NO3-) removal. This study applied synthetic stormwater with NO3- to three laboratory columns with underdrains located at the bottom, middle, or top of a 32 cm thick gravel-woodchip IWS. Under steady state conditions, underdrain nitrogen removal demonstrated a positive linear relationship with increasing hydraulic residence time (HRT). For a 1 cm/h hydraulic loading rate (HLR), nitrogen removal efficiency increased from 52 to 99% as underdrain height moved from the top to the bottom. Despite identical IWS thickness across columns, immobilize zones below the middle and top underdrains limited the steady state nitrogen removal. Dual isotopes in NO3- also indicated denitrification occurred in mobile zones and showed little or no denitrification in immobile zones due to limited mass transport. Transient flow conditions were applied, to mimic storms, followed by dry conditions. Lower effluent nitrogen concentrations and mass fluxes were observed from the bottom underdrain across the range of HLRs tested (1 to 5 cm/h) but performance of all three underdrains converged after the application of one pore volume. The top underdrain enhanced mixing between new incoming low-DOC stormwater and old IWS water with high-DOC which minimized effluent DOC concentrations. NO3- isotope enrichment factors indicated denitrification during transient flow for all three underdrain heights and enrichment increased for the 5 cm/h HLR. For sites with narrow IWS geometries (width to depth ratio < 1), optimal underdrain height is likely located between the bottom and top of the IWS to promote mixing with old IWS water high in DOC and sustain denitrification during storms.

Competitive sorption of Cd, Cr, Cu, Ni, Pb and Zn from stormwater runoff by five low-cost sorbents; Effects of co-contaminants, humic acid, salinity and pH.

For a comprehensive estimation of metals removal by sorbents in stormwater systems, it is essential to evaluate the impacts of co-contaminants. However, most studies consider only metals (single or multiple), which may overestimate performance. This study employed a batch method to investigate the performance of five low-cost sorbents - coconut coir fiber (CCF), blast furnace slag (BFS), waste tire crumb rubber (WTCR), biochar (BC), and iron coated biochar (FeBC) - for simultaneous removal of Cd, Cr, Cu, Ni, Pb and Zn from simulated stormwater (SSW) containing other contaminants (nutrients and polycyclic aromatic hydrocarbons). BFS and CCF demonstrated the highest sorption capacity of all metals (> 95% removal) in all systems (single and multi-contaminant). However, the presence of other contaminants in solution reduced metals removal for other sorbents, as follows (highest to lowest removal): single-metal > multi-metal > multi-contaminant solutions, and removal efficiency ranking among metals was generally Cr~Cu~Pb > Ni > Cd > Zn. Humic acid (HA) negatively affected the metal sorption, likely due to the formation of soluble HA-metal complexes; NaCl concentration did not impact removal, but alkaline pH improved removal. These findings indicate that sorbents need to be tested under realistic stormwater solution chemistry including co-contaminants to appropriately characterize performance prior to implementation.

Environmental Sources, Chemistry, Fate, and Transport of Per- and Polyfluoroalkyl Substances: State of the Science, Key Knowledge Gaps, and Recommendations Presented at the August 2019 SETAC Focus Topic Meeting.

A Society of Environmental Toxicology and Chemistry (SETAC) Focused Topic Meeting (FTM) on the environmental management of per- and polyfluoroalkyl substances (PFAS) convened during August 2019 in Durham, North Carolina (USA). Experts from around the globe were brought together to critically evaluate new and emerging information on PFAS including chemistry, fate, transport, exposure, and toxicity. After plenary presentations, breakout groups were established and tasked to identify and adjudicate via panel discussions overarching conclusions and relevant data gaps. The present review is one in a series and summarizes outcomes of presentations and breakout discussions related to (1) primary sources and pathways in the environment, (2) sorption and transport in porous media, (3) precursor transformation, (4) practical approaches to the assessment of source zones, (5) standard and novel analytical methods with implications for environmental forensics and site management, and (6) classification and grouping from multiple perspectives. Outcomes illustrate that PFAS classification will continue to be a challenge, and additional pressing needs include increased availability of analytical standards and methods for assessment of PFAS and fate and transport, including precursor transformation. Although the state of the science is sufficient to support a degree of site-specific and flexible risk management, effective source prioritization tools, predictive fate and transport models, and improved and standardized analytical methods are needed to guide broader policies and best management practices. Environ Toxicol Chem 2021;40:3234-3260. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Simultaneous removal of multiple polycyclic aromatic hydrocarbons (PAHs) from urban stormwater using low-cost agricultural/industrial byproducts as sorbents.

The potential of five low-cost and globally available sorbents, including three raw waste products - waste tire crumb rubber (WTCR), coconut coir fiber (CCF) and blast furnace slag (BFS) - and two modified materials - biochar (BC) and iron coated biochar (FeBC) - were evaluated for removing a mixture of polycyclic aromatic hydrocarbons (PAHs): pyrene (PYR), phenanthrene (PHE), acenaphthylene (ACY) and naphthalene (NAP) from simulated stormwater. The physicochemical characteristics of the sorbents were assessed by BET-N2 surface area, CHN elemental analysis, FTIR and scanning electron microscope (SEM-EDS). The experimental data were well described by both linear and Freundlich isotherm and pseudo-second order kinetic models. The adsorption rate was mainly controlled by the film diffusion mass transfer mechanism. The magnitude of PAHs partition coefficients (Kd) followed the order of BC > FeBC > WTCR > CCF â‰« BFS, ranging from 80 to 390,000 L/kg. The sorption Kd values were positively correlated with both aromaticity of sorbents and octanol-water partition coefficients (Kow) of PAHs. Solution ionic strength and pH did not have significant effects on the sorption of PAHs by all sorbents. In contrast, humic acid, as dissolved organic carbon, decreased sorption capacities of WTCR and CCF, and increased sorption efficiency of BFS, which was confirmed with field-collected real stormwater. The hydrophobic π-π interactions were the main mechanism for the sorption of PAHs by various sorbents. These findings are promising for future development of cost-effective sorption filters for removal of hydrophobic organic pollutants from urban stormwater runoff.

Linking PFAS partitioning behavior in sewage solids to the solid characteristics, solution chemistry, and treatment processes.

Per- and polyfluoroalkyl substances (PFAS) have gained increasing attention due to the potential health risks that they present. Secondary sludge and biosolids are known as notable PFAS emission routes to the environment. In this study, partitioning behavior of 14 PFAS were investigated across four secondary wastewater treatment types (activated sludge, trickling filter, biological nutrient removal, and rotating biological contactor; n = 10) and three sludge stabilization methods (composting, aerobic digestion, and anaerobic digestion; n = 6). Batch experiments were conducted to evaluate how PFAS sorption to secondary sludge and biosolid was affected by various treatment methods, solid properties, and solution chemistry parameters. Insignificant differences in compound-specific partitioning coefficients (Kd) were observed among the four secondary treatment methods. However, sludge stabilization resulted in significantly different partitioning behavior among biosolid samples, in which anaerobically digested biosolids generally had significantly higher Kd values compared to aerobically digested and composted biosolids (anaerobic digestion > aerobic digestion > composting). Multiple linear regression models were developed to explain analyte-specific Kd values across the biosolid samples and identified that solid-specific property significance was as follows: protein fraction > organic matter fraction > lipid fraction. Stabilization generally decreased the PFAS sorption capacity relative to the secondary sludge samples. Furthermore, PFAS Kd increased with elevated calcium concentrations and ionic strengths and decreased with increasing pH values in sludge and biosolid samples. These findings could inform the decision-making process to reduce the release of PFAS to the environment.

Differential Effects of Clinically Relevant N- versus C-Terminal Truncating CDKN1A Mutations on Cisplatin Sensitivity in Bladder Cancer.

Muscle-invasive bladder cancer (MIBC) frequently harbors mutations in the CDKN1A gene, which encodes the tumor suppressor protein p21, with the majority of alterations truncating the peptide. The effect of these mutations is poorly understood. We hypothesized that after DNA-damaging events, cells deficient in p21 would be unable to halt the cell cycle and efficiently repair DNA damage, thus proceeding down the apoptotic pathway. We used synthetic CRISPR guide RNAs to ablate the whole peptide (sg12, targeting the 12th amino acid) or the C-terminal proliferating cell nuclear antigen (PCNA)-binding domain (sg109) to mimic different p21-truncating mutations compared with a negative control (sgGFP) in bladder cancer cell lines. Loss of detectable p21 and a stable truncated p21 peptide were identified in sg12 and sg109 single-cell clones, respectively. We found that p21-deficient cells (sg12) were sensitized to cisplatin, while cells harboring distally truncated p21 (sg12 clones) demonstrated enhanced cisplatin resistance. p21-deficient sg12 clones demonstrated less repair of DNA-platinum adducts and increased γ-H2AX foci after cisplatin exposure, suggesting there was persistent DNA damage after p21 loss. p21-deficient sg12 clones were also unable to prevent the activation of CDK1 after DNA damage, and therefore, continued through the cell cycle, resulting in replication fork collapse, potentially explaining the observed cisplatin sensitization. sg109 clones were neither unable to sequester PCNA nor localize p21 to the nucleus after DNA damage, potentially explaining the chemoresistant phenotype. Our findings suggest that different CDKN1A truncations have different and perhaps disparate biology, and that there may be a duality of effect on cisplatin sensitivity depending on mutation context. IMPLICATIONS: Some truncating CDKN1A mutations generate a retained peptide that may have neomorphic functions and affect cisplatin sensitivity in patients with bladder cancer.

Single versus multi-metal sulfide systems: The role of cysteine and complex environmental conditions.

The presence of dissolved organic matter (DOM) can impact metal sulfide (MeS) precipitation and mobility. Thiol containing ligands such as cysteine have been shown to be effective capping agents in single metal MeS studies, allowing NPs to persist in oxic environments. In this study, both single (Cd or Zn) and multi-MeS (Cu, Pb, Cd, Zn, and As) nanoparticle (NP) formation was characterized to understand the impact of the thiol cysteine (CYS) on early stage (3 h) MeS NP behavior. Short duration single metal batch experiments, in the absence and presence of CYS, confirmed that MeS species readily formed solids with limited dissolved fraction; however, multi-metal systems exhibited divergent behavior reflecting a wider range of NP sizes and an increased dissolved concentration. Multi-metal batch experiments revealed that metals were generally sequestered into MeS solids in accordance with MeS solubility products (i.e., from least to most soluble: Cu > Pb ~ Cd > Zn). CYS concentrations in excess of sulfide (10:1 CYS:S ratio) stabilized MeS within the Small NP size fraction (3.2 nm < d < 43 nm) and limited Pb, Cd, and Zn dissolution compared to molar ratios of 1:1. In the combined presence of CYS and Ca2+, multi-MeS particle aggregation increased substantially compared to monovalent systems. Dissolution increased for Pb and Zn as a function of matrix ionic strength whereas dissolved Cu trends changed as a function of cation valence state (e.g., Na+ vs. Ca2+). Most noteworthy, single-metal Zn and Cd batch experiments demonstrated that single-metal studies can overestimate MeS NP resistance to oxidative dissolution compared to multi-metal counterparts. Thus, caution should be taken when broadly applying mechanisms and rates elucidated from single-metal systems.

Iron-mediated degradation of ribosomes under oxidative stress is attenuated by manganese.

Protein biosynthesis is fundamental to cellular life and requires the efficient functioning of the translational machinery. At the center of this machinery is the ribosome, a ribonucleoprotein complex that depends heavily on Mg2+ for structure. Recent work has indicated that other metal cations can substitute for Mg2+, raising questions about the role different metals may play in the maintenance of the ribosome under oxidative stress conditions. Here, we assess ribosomal integrity following oxidative stress both in vitro and in cells to elucidate details of the interactions between Fe2+ and the ribosome and identify Mn2+ as a factor capable of attenuating oxidant-induced Fe2+-mediated degradation of rRNA. We report that Fe2+ promotes degradation of all rRNA species of the yeast ribosome and that it is bound directly to RNA molecules. Furthermore, we demonstrate that Mn2+ competes with Fe2+ for rRNA-binding sites and that protection of ribosomes from Fe2+-mediated rRNA hydrolysis correlates with the restoration of cell viability. Our data, therefore, suggest a relationship between these two transition metals in controlling ribosome stability under oxidative stress.

Long-term simulation of potentially toxic elements (PTEs) accumulation and breakthrough in infiltration-based stormwater management practices (SMPs).

Stormwater management practices (SMPs) rely on infiltration and adsorption capabilities of soil and vegetative cover to mitigate the harmful impacts of contaminants in stormwater runoff, including potentially toxic elements (PTEs). Under chemical equilibrium conditions, the soil-water distribution coefficient (Kd) quantifies the relationship between the solid and aqueous phase PTE concentrations, and thus the PTE removal efficiency and mobility through the SMP soil layers during the infiltration process. The SMP loading ratio (LR), the ratio of the drainage area to the SMP infiltration area, combined with runoff concentration determines SMP mass loading and is also expected to impact PTE transport. In this study, a simulation model was developed to investigate PTE breakthrough and build-up in SMP media, considering the impacts of Kd and LR. Eight PTEs were simulated (Cl-, Cr, Fe, Zn, Cu, As, Cd, and Pb), and Cl- was the only PTE that showed high mobility and reached the groundwater table (e.g., ~ 1 year for breakthrough). Conversely, other PTEs were effectively immobilized in the top ~60 cm of soil for a simulated lifespan of 20 years. Soil and porewater contaminant indices, as indicators of SMP lifespan, were estimated based on the ratio of PTE porewater and soil concentrations after 20 years to published standards, suggesting the following order of environmental significance (most concern to least): Cl- > Cr > As > Pb > Fe > Cu > Cd > Zn. After 20 years of simulated use, only Cl- pore water concentrations at the groundwater table exceeded regulatory values, with porewater contamination index values of 4 to 7.5. Chloride also exceeded the surficial media soil contamination index, as did As and Cr, though these exceedences were largely associated with media background concentrations. Generally, higher LR and Kd contributed to higher accumulation of PTEs in top layers; however, simulations showed that the combination of low LR and high Kd may result in lower PTE accumulation in the media, such that the PTE concentration in soil may decrease in deeper layers. In these scenarios, a notable fraction of PTE load was adsorbed on top layers and considerably lower PTE concentrations reached the lower layers. Sensitivity analysis revealed that dispersion, infiltration rate, and kinetically-limited sorption did not impact the PTE accumulation and mobility to a practical extent. The results from this simulation may be adapted to various environmental conditions to enhance the design and maintenance of SMPs.