Heavy Metal Bioaccumulation in Peruvian Food and Medicinal Products.

To better query regional sources of metal(loid) exposure in an under-communicated region, available scientific literature from 50 national universities (undergraduate and graduate theses and dissertations), peer-reviewed journals, and reports published in Spanish and English were synthesized with a focus on metal(loid) bioaccumulation in Peruvian food and medicinal products utilized locally. The study considered 16 metal(loid)s that are known to exert toxic impacts on humans (Hg, Al, Sb, As, Ba, Be, Cd, Cr, Sn, Ni, Ag, Pb, Se, Tl, Ti, and U). A total of 1907 individual analyses contained within 231 scientific publications largely conducted by Peruvian universities were analyzed. These analyses encompassed 239 reported species classified into five main food/medicinal groups-plants, fish, macroinvertebrates and mollusks, mammals, and "others" category. Our benchmark for comparison was the World Health Organization (Codex Alimentarius) standards. The organisms most frequently investigated included plants such as asparagus, corn, cacao, and rice; fish varieties like trout, tuna, and catfish; macroinvertebrates and mollusks including crab and shrimp; mammals such as alpaca, cow, chicken eggs, and milk; and other categories represented by propolis, honey, lichen, and edible frog. Bioaccumulation-related research increased from 2 to more than 25 publications per year between 2006 and 2022. The results indicate that Peruvian food and natural medicinal products can have dangerous levels of metal(loid)s, which can cause health problems for consumers. Many common and uncommon food/medicinal products and harmful metals identified in this analysis are not regulated on the WHO's advisory lists, suggesting the urgent need for stronger regulations to ensure public safety. In general, Cd and Pb are the metals that violated WHO standards the most, although commonly non-WHO regulated metals such as Hg, Al, As, Cr, and Ni are also a concern. Metal concentrations found in Peru are on many occasions much higher than what has been reported elsewhere. We conclude that determining the safety of food/medicinal products is challenging due to varying metal concentrations that are influenced not only by metal type but also geographical location. Given the scarcity of research findings in many regions of Peru, urgent attention is required to address this critical knowledge gap and implement effective regulatory measures to protect public health.

Estimating historical exposure to perfluoroalkyl acids in Security, Fountain, and Widefield Colorado: use of water-infrastructure blending and toxicokinetic models.

Drinking water can be a major source of poly- and perfluoroalkyl substance (PFAS) exposure for humans. The lack of historic data on PFAS drinking-water concentrations and consumption patterns are a limiting factor for developing estimates of past exposure. Here, in contribution to a community-scale PFAS health effects study near fire training facilities that contaminated a local aquifer with PFASs, we present a novel water-infrastructure, mass-balance mixing model coupled to a non-steady state, single-compartment toxicokinetic model that used Monte Carlo simulations to estimate the start of PFAS exposure in drinking water for individuals within three PFAS-impacted communities in El Paso County, Colorado. Our modeling focused on perfluorohexane sulfonic acid (PFHxS) because median serum PFHxS concentrations in a sample of local residents (n = 213) were twelve times the median observed in the U.S. National Health and Nutrition Examination Survey (2015-2016). Modeling results for study participants were grouped according to their community of residence, revealing a median start of exposure for the town of Fountain of 1998 (25-75% interquartile range [IQR], 1992 to 2010), 2006 (IQR 1995 to 2012) for Security, and 2009 (IQR 1996-2012) for Widefield. Based on the towns' locations relative to an identified hydraulically upgradient PFAS source, the modeled exposure sequencing does not completely align with this conceptual flow model, implying the presence of an additional PFAS source for the groundwater between Widefield and Fountain.

Simulated leaching of PFAS from land-applied municipal biosolids at agricultural sites.

Biosolids are an important resource for agricultural practice but have recently received increased focus as a potential source of per- and polyfluoroalkyl substances (PFAS) in the environment. Few studies have investigated the transport of PFAS through the unsaturated zone under conditions relevant to biosolids application sites. Herein, the unsaturated flow and transport model HYDRUS is used to evaluate the leaching of per- and polyfluoroalkyl substances (PFAS) from land-applied biosolids used in agricultural practice to determine the impacts of PFAS leaching on underlying groundwater resources. This numerical case study was based on conditions and operations at two test sites in central Illinois where biosolids were applied at agronomic rates and where PFAS contents and desorption characteristics were previously characterized. Each site possessed different vadose zone soil textural heterogeneity. Simulations were performed under actual present-day meteorological conditions and extended 150 years beyond the initial biosolids application. These long-term simulations demonstrate how soil equilibrium sorption/desorption processes within the biosolids-amended surface soils effectively control the transport rate of individual PFAS to groundwater. Air-water interfacial (AWI) adsorption, which is sometimes considered to be a significant source of PFAS retention in vadose zone soils, was observed to have minimal impacts on PFAS leaching rates within the biosolids-amended surface soils at these sites. Additionally, the impact of AWI adsorption was found to be most significant for PFAS transport within the underlying vadose zone soils when these soils were more texturally homogeneous and considerably less significant within the texturally heterogeneous soils represented herein. The results of multiple long-term simulations were used to develop an empirical equation that relates predicted maximum PFAS pore-water concentrations reaching the saturated zone with changes in PFAS concentrations in the biosolids-amended soil for various biosolids re-application events. This approach is shown to be very useful in developing site-specific PFAS soil screening levels and/or maximum leachate levels for PFAS in support of establishing best management practices (BMPs) for land application of biosolids.

Comparison of methods to estimate air-water interfacial areas for evaluating PFAS transport in the vadose zone.

When performing calculations or numerical simulations for the fate and transport of PFAS and other surface-active solutes in the vadose zone, accurately representing the relationship between the area of the air-water interfaces (Aaw) as a function of water saturation (Sw), and changes in that relationship resulting from changes in soil texture, are equally important as accurately characterizing interfacial adsorption coefficients and the concentration dependence for PFAS solutes. This is true because the magnitude of the Aaw directly governs the degree of air-water interfacial adsorption, which contributes to the transport retardation of these solutes within unsaturated porous media. Herein, a well-known thermodynamic-based model for predicting the Aaw-Sw relationship is evaluated through comparisons to literature data collected using various measurement techniques for model sands and a limited number of soils using data collected from the current published literature. This predictive model, herein termed the Leverett thermodynamic model (LTM), relies on the characterization of the soil-water retention curve (SWRC) for a given soil, using the van Genuchten (VG) equation for the pressure head-vs-Sw relationship. Therefore, methods to estimate the VG equation parameters are also compared as to the Aaw-Sw relationships predicted. Comparisons suggest that the LTM provides the best estimate of the actual Aaw-Sw relationships for water containing non-surface-active solutes. Because PFAS solutes are also surface-active, Aaw measurement methods utilizing surface-active tracers are considered to provide the most accurate representation of the Aaw-Sw relationship for these solutes. Differences between Aaw-Sw relationships derived from tracer methods and the LTM are described in relation to media surface roughness effects. Based on the available literature data, a practical empirical model is proposed to adjust the LTM prediction to account for the effects of surface roughness on the magnitude of the Aaw for surface-active solutes. Finally, example retention calculations are performed to demonstrate the sensitivity of the predicted Aaw-Sw relationship on the vadose zone transport of of a representative PFAS, perfluorooctane sulfonate.

Modeling PFAS Fate and Transport in Groundwater, with and Without Precursor Transformation.

Groundwater professionals require tools to evaluate a variety of technical issues related to per- and polyfluoroalkyl substances (PFAS). These include the potential impact of PFAS precursors on groundwater plumes of perfluoroalkyl acids (PFAAs). Numerical modeling results show that, by adjusting the mass loading rate, source zones with or without a precursor can produce similar PFAA plumes. However, if a precursor is present, it can impact PFAA plume concentrations and extend PFAA plume durations by decades. Additional research regarding in situ precursor transformation rates-and improvements in source area characterization-will further advance the predictive value of modeling.

Air-water interfacial adsorption coefficients for PFAS when present as a multi-component mixture.

Surface tension isotherms and calculated air-water interfacial (AWI) adsorption data are presented for solution mixtures of per- and polyfluoroalkyl substances (PFAS), specifically a series of binary and one ternary mixtures of homologous linear perfluorocarboxylic acids (PFCAs) in a simulated groundwater, and two 8-component mixtures containing both PFCAs and linear perfluoroalkane sulfonates (PFSAs). In all cases, non-ideal competitive adsorption was observed that favored the most surface-active component(s) of the solution mixture. The multi-component extended Langmuir (EL) isotherm model was observed to accurately predict the competitive adsorption observed in the binary and ternary PFCA solution mixtures. However, the predictive utility of the EL model was observed to diminish when mixtures contained both PFCAs and PFSAs, which differ in their hydrophile structure, resulting in overpredictions and underpredictions of the AWI adsorption isotherms derived from measured data depending on the specific components present in the solution mixtures. Observations indicate that the individual component adsorptive affinities for the AWI can change in response to competitive preferential adsorption as their solution concentrations increase that is not being captured by the EL model. Our results demonstrate that alternative mathematical models are needed that support concentration dependent affinity coefficients for non-similar mixtures of PFAS, such that the transport of individual target PFAS components within a larger mixture of components can be accurately predicted across a wider range of solution concentration.

Subsurface transport potential of perfluoroalkyl acids (PFAAs): Column experiments and modeling.

Transport of ten perfluoroalkyl acids (PFAAs) was studied with one-dimensional (1-D) saturated column experiments using four soil types with an organic carbon fraction (foc) range of ~0-0.045. Columns were operated under conditions relevant to aqueous film-forming foam (AFFF)-impacted fire protection training areas to determine the ability of equilibrium transport parameters to describe 1-D PFAA transport, if rate-limited sorption influences PFAA transport, and if kinetic parameters can be used to evaluate factors causing rate-limited sorption. Results of initial screening of PFAA breakthrough found that over half of the breakthrough curves deviated from equilibrium transport and merited further investigation. Subsequent analysis showed that, in many cases, these deviations could be accounted for by considering the range of applicable equilibrium Kd values (i.e. based on standard deviation) applicable to the solid phase. Thus, transport of the majority of PFAAs in 3 soils with foc of 0-0.017 was not impacted by rate-limited sorption. Further, low sorption led to transport that was essentially simultaneous for the majority of PFAAs in these porous media. Exceptions were observed for long-chain PFAAs, and also in a fourth soil with foc of 0.045, which indicated the potential for rate-limited sorption to impact transport in some scenarios. Subsequent flow interruption experiments isolating kinetic behavior confirmed rate-limited sorption caused nonequilibrium transport. Linear free energy relationships (LFERs) developed in previous work to predict the inverse relationship between mass transfer coefficients (k) and sorption parameters (i.e., Kd) were used to estimate values of k for PFAAs in this study. Resulting k values were 10-3 to 10-8 h-1, consistent with previously measured kinetic parameters for other polar and anionic compounds. Models incorporating estimated k values resulted in improved predictions of breakthrough observed in nonequilibrium scenarios (R2 0.83-0.98), but k values will require further validation prior to broader application. This work illustrates rate-limited sorption considerations are needed to describe 1-D column saturated transport for some PFAAs and solid phases. At field scales, subsurface heterogeneity and PFAA precursor transformation may be equally or even more important in determining saturated PFAA transport, but kinetic parameters in this study may help to determine relative contributions of rate-limited sorption to overall transport.

Evaluating air-water and NAPL-water interfacial adsorption and retention of Perfluorocarboxylic acids within the Vadose zone.

The release and transport of linear perfluorocarboxylic acids (PFCA) within the vadose-zone beneath per- and polyfluoroalkyl substance (PFAS)- and non-aqueous phase liquid (NAPL)-contaminated source areas is influenced by multi-phase interfacial retention phenomena. Conceptually, interfacial adsorption results in retardation of PFCA velocities in subsurface multiphase systems. However, site hydrochemical factors influencing interfacial adsorption are not yet fully elucidated. Herein, air-water and NAPL-water interfacial tension isotherms were prepared for six homologous PFCAs of environmental significance for deionized water and five synthetic groundwaters of increasing ionic strength. The isotherms were successfully modeled by the Langmuir-Szyskowski equation and parameters used to fit the measured data are provided. Concentration-dependent interfacial adsorption coefficients and retardation factors are also provided for each PFCA and ionic strength condition and are evaluated to assess their significance. Simplifying relationships for predicting interfacial adsorption based on PFCA chain length were found to be less appropriate for natural groundwaters that contain a mixture of dissolved divalent and monovalent ions. Air-water interfacial (AWI) adsorption increased in a threshold manner with ionic strength from 0 to 6 mM, whereafter further adsorption was marginal. PFCA retention within water-unsaturated porous media is shown to depend on a number of inter-related factors and conditions that complicate the use of retardation factors within analytical models typically used for predicting transport rates under field conditions. Numerical simulation is thus necessary to model fundamental fate and transport processes. Mathematical relationships for incorporating interfacial adsorption in future and existing unsaturated flow and transport models are described.

Evaluating emerging organic contaminant removal in an engineered hyporheic zone using high resolution mass spectrometry.

The hyporheic zone (HZ), located at the interface of surface and groundwater, is a natural bioreactor for attenuation of chemical contaminants. Engineered HZs can be incorporated into stream restoration projects to enhance hyporheic exchange, with flowpaths optimized to promote biological habitat, water quantity, and water quality improvements. Designing HZs for in-stream treatment of stormwater, a significant source of flow and contaminant loads to urban creeks, requires assessment of both the hydrology and biogeochemical capacity for water quality improvement. Here, we applied tracer tests and high resolution mass spectrometry (HRMS) to characterize an engineered hyporheic zone unit process, called a hyporheic design element (HDE), in the Thornton Creek Watershed in Seattle, WA. Dye, NaCl, and bromide were used to hydrologically link downwelling and upwelling zones and estimate the hydraulic retention time (HRT) of hyporheic flowpaths. We then compared water quality improvements across hydrologically-linked surface and hyporheic flowpaths (3-5 m length; ∼30 min to >3 h) during baseflow and stormflow conditions. We evaluated fate outcomes for 83 identified contaminants during stormflow, including those correlated with an urban runoff mortality syndrome in coho salmon. Non-target HRMS analysis was used to assess holistic water quality improvements and evaluate attenuation mechanisms. The data indicated substantial water quality improvement in hyporheic flowpaths relative to surface flow and improved contaminant removal with longer hyporheic HRT (for ∼1900 non-target compounds detected during stormflow, <17% were attenuated >50% via surface flow vs. 59% and 78% via short and long hyporheic residence times, respectively), and strong contributions of hydrophobic sorption towards observed contaminant attenuation.

Performance of Engineered Streambeds for Inducing Hyporheic Transient Storage and Attenuation of Resazurin.

Several U.S. programs provide financial incentives for stream restoration to improve degraded water quality. These efforts prioritize hyporheic zone (HZ) restoration to enhance contaminant attenuation, but no stream restoration or stormwater best management practice (BMP) explicitly tailors hyporheic residence times to target specific contaminants of concern. Here we present the first physical demonstration of a new BMP called Biohydrochemical Enhancements for Streamwater Treatment (BEST). BEST are subsurface modules that use hydraulic conductivity modifications to drive hyporheic exchange and control residence times, combined with reactive geomedia to increase HZ reaction rates. Experiments were conducted in 15-m long outdoor flumes: one all-sand control, the other with BEST modules. Sodium chloride (conservative tracer) and resazurin (surrogate for a reactive pollutant) injections were conducted, with observations analyzed by stream transient storage models. Results demonstrated that BEST increased the effective HZ size and resazurin transformation both by ∼50% compared to the control. Numerical simulations of extended reach lengths showed that BEST could achieve 1-log removal of resazurin in 111 m, versus 172 m in the control, and 414 m and 683 m in two numerically simulated urban streams. These results emphasize the potential of BEST as a novel HZ BMP to improve streamwater quality.

Microbial community composition of a hydrocarbon reservoir 40 years after a CO2 enhanced oil recovery flood.

Injecting CO2 into depleted oil reservoirs to extract additional crude oil is a common enhanced oil recovery (CO2-EOR) technique. However, little is known about how in situ microbial communities may be impacted by CO2 flooding, or if any permanent microbiological changes occur after flooding has ceased. Formation water was collected from an oil field that was flooded for CO2-EOR in the 1980s, including samples from areas affected by or outside of the flood region, to determine the impacts of CO2-EOR on reservoir microbial communities. Archaea, specifically methanogens, were more abundant than bacteria in all samples, while identified bacteria exhibited much greater diversity than the archaea. Microbial communities in CO2-impacted and non-impacted samples did not significantly differ (ANOSIM: Statistic R = -0.2597, significance = 0.769). However, several low abundance bacteria were found to be significantly associated with the CO2-affected group; very few of these species are known to metabolize CO2 or are associated with CO2-rich habitats. Although this study had limitations, on a broad scale, either the CO2 flood did not impact the microbial community composition of the target formation, or microbial communities in affected wells may have reverted back to pre-injection conditions over the ca. 40 years since the CO2-EOR.

Environmental Drivers of Differences in Microbial Community Structure in Crude Oil Reservoirs across a Methanogenic Gradient.

Stimulating in situ microbial communities in oil reservoirs to produce natural gas is a potentially viable strategy for recovering additional fossil fuel resources following traditional recovery operations. Little is known about what geochemical parameters drive microbial population dynamics in biodegraded, methanogenic oil reservoirs. We investigated if microbial community structure was significantly impacted by the extent of crude oil biodegradation, extent of biogenic methane production, and formation water chemistry. Twenty-two oil production wells from north central Louisiana, USA, were sampled for analysis of microbial community structure and fluid geochemistry. Archaea were the dominant microbial community in the majority of the wells sampled. Methanogens, including hydrogenotrophic and methylotrophic organisms, were numerically dominant in every well, accounting for, on average, over 98% of the total Archaea present. The dominant Bacteria groups were Pseudomonas, Acinetobacter, Enterobacteriaceae, and Clostridiales, which have also been identified in other microbially-altered oil reservoirs. Comparing microbial community structure to fluid (gas, water, and oil) geochemistry revealed that the relative extent of biodegradation, salinity, and spatial location were the major drivers of microbial diversity. Archaeal relative abundance was independent of the extent of methanogenesis, but closely correlated to the extent of crude oil biodegradation; therefore, microbial community structure is likely not a good sole predictor of methanogenic activity, but may predict the extent of crude oil biodegradation. However, when the shallow, highly biodegraded, low salinity wells were excluded from the statistical analysis, no environmental parameters could explain the differences in microbial community structure. This suggests that the microbial community structure of the 5 shallow, up-dip wells was different than the 17 deeper, down-dip wells. Also, the 17 down-dip wells had statistically similar microbial communities despite significant changes in environmental parameters between oil fields. Together, this implies that no single microbial population is a reliable indicator of a reservoir's ability to degrade crude oil to methane, and that geochemistry may be a more important indicator for selecting a reservoir suitable for microbial enhancement of natural gas generation.

The influence of a non-aqueous phase liquid (NAPL) and chemical oxidant application on perfluoroalkyl acid (PFAA) fate and transport.

One dimensional column experiments were conducted using saturated porous media containing residual trichloroethylene (TCE) to understand the effects of non-aqueous phase liquids (NAPLs) and chemical oxidation on perfluoroalkyl acid (PFAA) fate and transport. Observed retardation factors and data from supporting batch studies suggested that TCE provides additional sorption capacity that can increase PFAA retardation (i.e., decreased mobility), though the mechanisms remain unclear. Treatment with persulfate activated with FeCl2 and citric acid, catalyzed hydrogen peroxide (CHP), or permanganate did not result in oxidative transformations of PFAAs. However, impacts on PFAA sorption were apparent, and enhanced sorption was substantial in the persulfate-treated columns. In contrast, PFAA transport was accelerated in permanganate- and CHP-treated columns. Ultimately, PFAA transport in NAPL contaminated groundwater is likely influenced by porous media properties, NAPL characteristics, and water quality properties, each of which can change due to chemical oxidant treatment. For contaminated sites for which ISCO is a viable treatment option, changes to PFAA transport and the implications thereof should be included as a component of the remediation evaluation and selection process.

Repurposing and Rescuing of Mibefradil, an Antihypertensive, for Cancer: A Case Study.

The expanding "valley of death" in drug development is leaving potentially life-saving new chemical entities and molecular targets fallow. This situation is forcing early-stage companies to think creatively about moving their technologies forward, especially as institutional investors show more interest in later stages of development. Drug repurposing, a strategy to examine existing drugs for therapeutic value against different diseases, is an emerging method to bring an off-market drug back onto the market. Tau Therapeutics LLC identified the role of T-type calcium channel blockers (Cav3) in cancer proliferation, but the company was unable to attract funding while having both a nonvalidated drug target and new chemical entities. To change the risk profile of the company, Tau set out to repurpose the known Cav3 drug mibefradil as a proof of concept for the treatment of cancer. Mibefradil was launched for hypertension in the 1990s but withdrawn because of drug-drug interactions. A new sequential combination treatment, termed Interlaced Therapy™, uses short-term administration of mibefradil to enhance the overall therapeutic potential of conventional anticancer agents. Mibefradil is currently in a phase Ib clinical trial with the National Cancer Institute (NCI) Adult Brain Tumor Consortium. Mibefradil has been repurposed from an abandoned antihypertensive to a targeted solid tumor treatment, and it has been rescued from drug-drug interactions by using short-term dose exposure. Tau is using the early success of mibefradil as a proof of concept to build a platform technology of Cav3 blockers for broad antitumor applications in combination with new targeted cancer therapies, well-established chemotherapies, and radiation.

Effects of chemical oxidants on perfluoroalkyl acid transport in one-dimensional porous media columns.

In situ chemical oxidation (ISCO) is a remediation approach that is often used to remediate soil and groundwater contaminated with fuels and chlorinated solvents. At many aqueous film-forming foam-impacted sites, perfluoroalkyl acids (PFAAs) can also be present at concentrations warranting concern. Laboratory experiments were completed using flow-through one-dimensional columns to improve our understanding of how ISCO (i.e., activated persulfate, permanganate, or catalyzed hydrogen peroxide) could affect the fate and transport of PFAAs in saturated porous media. While the resultant data suggest that standard ISCO is not a viable remediation strategy for PFAA decomposition, substantial changes in PFAA transport were observed upon and following the application of ISCO. In general, activated persulfate decreased PFAA transport, while permanganate and catalyzed hydrogen peroxide increased PFAA transport. PFAA sorption increased in the presence of increased aqueous polyvalent cation concentrations or decreased pH. The changes in contaminant mobility were greater than what would be predicted on the basis of aqueous chemistry considerations alone, suggesting that the application of ISCO results in changes to the porous media matrix (e.g., soil organic matter quality) that also influence transport. The application of ISCO is likely to result in changes in PFAA transport, where the direction (increased or decreased transport) and magnitude are dependent on PFAA characteristics, oxidant characteristics, and site-specific factors.

Metal fate and partitioning in soils under bark beetle-killed trees.

Recent mountain pine beetle infestation in the Rocky Mountains of North America has killed an unprecedented acreage of pine forest, creating an opportunity to observe an active re-equilibration in response to widespread land cover perturbation. This work investigates metal mobility in beetle-impacted forests using parallel rainwater and acid leaches to estimate solid-liquid partitioning coefficients and a complete sequential extraction procedure to determine how metals are fractionated in soils under trees experiencing different phases of mortality. Geochemical model simulations analyzed in consideration with experimental data provide additional insight into the mechanisms controlling metal complexation. Metal and base-cation mobility consistently increased in soils under beetle-attacked trees relative to soil under healthy trees. Mobility increases were more pronounced on south facing slopes and more strongly correlated to pH under attacked trees than under healthy trees. Similarly, soil moisture was significantly higher under dead trees, related to the loss of transpiration and interception. Zinc and cadmium content increased in soils under dead trees relative to living trees. Cadmium increases occurred predominantly in the exchangeable fraction, indicating increased mobilization potential. Relative increases of zinc were greatest in the organic fraction, the only fraction where increases in copper were observed. Model results reveal that increased organic complexation, not changes in pH or base cation concentrations, can explain the observed differences in metal partitioning for zinc, nickel, cadmium, and copper. Predicted concentrations would be unlikely to impair human health or plant growth at these sites; however, higher exchangeable metals under beetle-killed trees relative to healthy trees suggest a possible decline in riverine ecosystem health and water quality in areas already approaching criteria limits and drinking water standards. Impairment of water quality in important headwater streams from the increased potential for metal mobilization and storage will continue to change as beetle-killed trees decompose and forests begin to recover.

Changes in metal mobility associated with bark beetle-induced tree mortality.

Recent large-scale beetle infestations have caused extensive mortality to conifer forests resulting in alterations to dissolved organic carbon (DOC) cycling, which in turn can impact metal mobility through complexation. This study analyzed soil-water samples beneath impacted trees in concert with laboratory flow-through soil column experiments to explore possible impacts of the bark beetle infestation on metal release and transport. The columns mimicked field conditions by introducing pine needle leachate and artificial rainwater through duplicate homogenized soil columns and measuring effluent metal (focusing on Al, Cu, and Zn) and DOC concentrations. All three metals were consistently found in higher concentrations in the effluent of columns receiving pine needle leachate. In both the field and laboratory, aluminum mobility was largely correlated with the hydrophobic fraction of the DOC, while copper had the largest correlation with total DOC concentrations. Geochemical speciation modeling supported the presence of DOC-metal complexes in column experiments. Copper soil water concentrations in field samples supported laboratory column results, as they were almost twice as high under grey phase trees than under red phase trees further signifying the importance of needle drop. Pine needle leachate contained high concentrations of Zn (0.1 mg l(-1)), which led to high effluent zinc concentrations and sorption of zinc to the soil matrix representing a future potential source for release. In support, field soil-water samples underneath beetle-impacted trees where the needles had recently fallen contained approximately 50% more zinc as samples from under beetle-impacted trees that still held their needles. The high concentrations of carbon in the pine needle leachate also led to increased sorption in the soil matrix creating the potential for subsequent carbon release. While unclear if manifested in adjacent surface waters, these results demonstrate an increased potential for Zn, Cu, and Al mobility, along with increased deposition of metals and carbon beneath beetle-impacted trees.

Metal release from sandstones under experimentally and numerically simulated CO2 leakage conditions.

Leakage of CO2 from a deep storage formation into an overlying potable aquifer may adversely impact water quality and human health. Understanding CO2-water-rock interactions is therefore an important step toward the safe implementation of geologic carbon sequestration. This study targeted the geochemical response of siliclastic rock, specifically three sandstones of the Mesaverde Group in northwestern Colorado. To test the hypothesis that carbonate minerals, even when present in very low levels, would be the primary source of metals released into a CO2-impacted aquifer, two batch experiments were conducted. Samples were reacted for 27 days with water and CO2 at partial pressures of 0.01 and 1 bar, representing natural background levels and levels expected in an aquifer impacted by a small leakage, respectively. Concentrations of major (e.g., Ca, Mg) and trace (e.g., As, Ba, Cd, Fe, Mn, Pb, Sr, U) elements increased rapidly after CO2 was introduced into the system, but did not exceed primary Maximum Contaminant Levels set by the U.S. Environmental Protection Agency. Results of sequential extraction suggest that carbonate minerals, although volumetrically insignificant in the sandstone samples, are the dominant source of mobile metals. This interpretation is supported by a simple geochemical model, which could simulate observed changes in fluid composition through CO2-induced calcite and dolomite dissolution.

New Conceptual Model for Soil Treatment Units: Formation of Multiple Hydraulic Zones during Unsaturated Wastewater Infiltration.

Onsite wastewater treatment systems are commonly used in the United States to reclaim domestic wastewater. A distinct biomat forms at the infiltrative surface, causing resistance to flow and decreasing soil moisture below the biomat. To simulate these conditions, previous modeling studies have used a two-layer approach: a thin biomat layer (1-5 cm thick) and the native soil layer below the biomat. However, the effect of wastewater application extends below the biomat layer. We used numerical modeling supported by experimental data to justify a new conceptual model that includes an intermediate zone (IZ) below the biomat. The conceptual model was set up using Hydrus 2D and calibrated against soil moisture and water flux measurements. The estimated hydraulic conductivity value for the IZ was between biomat and the native soil. The IZ has important implications for wastewater treatment. When the IZ was not considered, a loading rate of 5 cm d resulted in an 8.5-cm ponding. With the IZ, the same loading rate resulted in a 9.5-cm ponding. Without the IZ, up to 3.1 cm d of wastewater could be applied without ponding; with the IZ, only up to 2.8 cm d could be applied without ponding. The IZ also plays a significant role in soil moisture distribution. Without the IZ, near-saturation conditions were observed only within the biomat, whereas near-saturation conditions extended below the biomat with the IZ. Accurate prediction of ponding is important to prevent surfacing of wastewater. The degree of water and air saturation influences pollutant treatment efficiency through residence time, volatility, and biochemical reactions.

Geochemical implications of brine leakage into freshwater aquifers.

CO(2) injection into deep saline formations as a way to mitigate climate change raises concerns that leakage of saline waters from the injection formations will impact water quality of overlying aquifers, especially underground sources of drinking water (USDWs). This paper aims to characterize the geochemical composition of deep brines, with a focus on constituents that pose a human health risk and are regulated by the U.S. Environmental Protection Agency (USEPA). A statistical analysis of the NATCARB brine database, combined with simple mixing model calculations, show total dissolved solids and concentrations of chloride, boron, arsenic, sulfate, nitrate, iron and manganese may exceed plant tolerance or regulatory levels. Twelve agricultural crops evaluated for decreased productivity in the event of brine leakage would experience some yield reduction due to increased TDS at brine-USDW ratios of < 0.1, and a 50% yield reduction at < 0.2 brine-USDW ratio. A brine-USDW ratio as low as 0.004 may result in yield reduction in the most sensitive crops. The USEPA TDS secondary standard is exceeded at a brine fraction of approximately 0.002. To our knowledge, this is the first study to consider agricultural impacts of brine leakage, even though agricultural withdrawals of groundwater in the United States are almost three times higher than public and domestic withdrawals.