Protection Agency Maximum Contaminant Level Research Articles

Robust and tunable performance of a cell-free biosensor encapsulated in lipid vesicles.

Cell-free systems have enabled the development of genetically encoded biosensors to detect a range of environmental and biological targets. Encapsulation of these systems in synthetic membranes to form artificial cells can reintroduce features of the cellular membrane, including molecular containment and selective permeability, to modulate cell-free sensing capabilities. Here, we demonstrate robust and tunable performance of a transcriptionally regulated, cell-free riboswitch encapsulated in lipid membranes, allowing the detection of fluoride, an environmentally important molecule. Sensor response can be tuned by varying membrane composition, and encapsulation protects from sensor degradation, facilitating detection in real-world samples. These sensors can detect fluoride using two types of genetically encoded outputs, enabling detection of fluoride at the Environmental Protection Agency maximum contaminant level of 0.2millimolars. This work demonstrates the capacity of bilayer membranes to confer tunable permeability to encapsulated, genetically encoded sensors and establishes the feasibility of artificial cell platforms to detect environmentally relevant small molecules.

Threonine Phosphorylation of an Electrochemical Peptide-Based Sensor to Achieve Improved Uranyl Ion Binding Affinity

We have successfully designed a uranyl ion (U(VI)-specific peptide and used it in the fabrication of an electrochemical sensor. The 12-amino acid peptide sequence, (n) DKDGDGYIpTAAE (c), originates from calmodulin, a Ca(II)-binding protein, and contains a phosphothreonine that enhances the sequence's affinity for U(VI) over Ca(II). The sensing mechanism of this U(VI) sensor is similar to other electrochemical peptide-based sensors, which relies on the change in the flexibility of the peptide probe upon interacting with the target. The sensor was systematically characterized using alternating current voltammetry (ACV) and cyclic voltammetry. Its limit of detection was 50 nM, which is lower than the United States Environmental Protection Agency maximum contaminant level for uranium. The signal saturation time was ~40 min. In addition, it showed minimal cross-reactivity when tested against nine different metal ions, including Ca(II), Mg(II), Pb(II), Hg(II), Cu(II), Fe(II), Zn(II), Cd(II), and Cr(VI). Its reusability and ability to function in diluted aquifer and drinking water samples were further confirmed and validated. The response of the sensor fabricated with the same peptide sequence but with a nonphosphorylated threonine was also analyzed, substantiating the positive effects of threonine phosphorylation on U(VI) binding. This study places emphasis on strategic utilization of non-standard amino acids in the design of metal ion-chelating peptides, which will further diversify the types of peptide recognition elements available for metal ion sensing applications.

Survey of 226Ra/228Ra and inorganic constituents in Iowa private drinking water wells

AbstractRadium is a naturally‐occurring radioactive element found in Upper Midwest aquifers, yet exposure risks for unregulated water sources in this region are unknown. A survey of 226/228Ra and other inorganic constituents in 94 private wells was conducted in 2019 across 10 Iowa counties. Within private wells, 53% measured below minimum detectable activity whereas 6.3% have 226/228Ra levels above the United States Environmental Protection Agency Maximum Contaminant Level. 226/228Ra occurrence was not associated with well‐depth or chemical surrogates, but were generally consistent with the lithology and historical water quality trends for aquifers. In 2020, 11 of the 226/228Ra‐impacted wells were re‐sampled to assess the efficacy of in‐home water treatment. Water softeners reduced 226/228Ra to non‐detectable activities, but other inorganic constituents persisted and their removal required more advanced treatment. This study suggests that 226/228Ra occurrence in private wells can reasonably be anticipated from public water supply data if reliable information is available to identify the source aquifer.

Removal of uranium from contaminated groundwater using monorhamnolipids and ion flotation

Mining of uranium for defense-related purposes has left a substantial legacy of pollution that threatens human and environmental health. Contaminated waters in the arid southwest are of particular concern, as water resource demand and water scarcity issues become more pronounced. The development of remediation strategies to treat uranium impacted waters will become increasingly vital to meet future water needs. Ion flotation is one technology with the potential to address legacy uranium contamination. The green biosurfactant rhamnolipid has been shown to bind uranium and act as an effective collector in ion flotation. In this study, uranium contaminated groundwater (∼440 μg L−1 U) from the Monument Valley processing site in northeast Arizona was used as a model solution to test the uranium removal efficacy of ion flotation with biosynthetic (bio-mRL) and three synthetic monorhamnolipids with varying hydrophobic chain lengths: Rha-C10-C10, Rha-C12-C12, and Rha-C14-C14. At the groundwater's native pH 8, and at an adjusted pH 7, no uranium was removed from solution by any collector. However, at pH 6.5 bio-mRL and Rha-C10-C10 removed 239.2 μg L−1 and 242.4 μg L−1 of uranium, respectively. By further decreasing the pH to 5.5, bio-mRL was able to reduce the uranium concentration to near or below the Environmental Protection Agency maximum contaminant level of 30 μg L−1. For the Rha-C12-C12 and Rha-C14-C14 collector ligands, decreasing the pH to 7 or below reduced the foam stability and quantity, such that these collectors were not suitable for treating this groundwater. To contextualize the results, a geochemical analysis of the groundwater was conducted, and a consideration of uranium speciation is described. Based on this study, the efficacy of monorhamnolipid-based ion flotation in real world groundwater has been demonstrated with suitable solution conditions and collectors identified.

Water as a relevant source of inorganic arsenic exposure in U.S. cities

BACKGROUND AND AIM: Water arsenic represents a health concern for US residents served by community water systems (CWS) exceeding the Environmental Protection Agency (EPA) Maximum Contaminant Level (MCL) of 10 µg/L, and for residents reliant on unregulated private wells. Little is known on the contribution of CWS arsenic exposures below the MCL, particularly in urban areas. We evaluated whether water arsenic is a relevant source of urinary arsenic in urban settings in the Multi-Ethnic Study of Atherosclerosis (MESA). METHODS: We examined the association of CWS arsenic with urinary arsenic concentrations (µg/L) for 910 MESA participants from Baltimore, Chicago, Los Angeles, New York City, St. Paul, MN, and Winston-Salem, NC. We assigned three-year population weighted averages of CWS arsenic concentrations using 2006-2008 EPA data (before MCL implementation) to participants by zip code. Dietary information and urinary samples were collected in 2000-2002. Urinary arsenic species were measured using HPLC-ICPMS. We accounted for seafood intake using a residual based method. Linear models adjusted for race/ethnicity, income, smoking status, diet (rice) and urinary creatinine to account for urine dilution. RESULTS:CWS arsenic levels ranged from 0.5 µg/L (LOD) in several cities to 3.05 µg/L in Chicago (median 0.44 µg/L). CWS arsenic was positively correlated (p 0.05) with urinary inorganic arsenic (Spearman’s rho 0.11), dimethylarsinate (DMA) (0.09), monomethylarsonate (MMA) (0.16) and their sum (0.10). In adjusted models, a 1 µg/L change in CWS arsenic was associated with 1.29 (95%CI 1.01, 1.64) higher inorganic arsenic and 1.19 (1.03, 1.38) higher MMA. The association with DMA, sum of inorganic and methylated species was not statistically significant. CONCLUSIONS:Drinking water arsenic is a relevant source of exposure and internal dose in US urban areas, determined by urinary arsenic biomarkers. Research is needed to determine health implications of chronic exposure to water arsenic below the MCL, including vulnerable subpopulations. KEYWORDS: arsenic, drinking water, exposure assessment, environmental epidemiology

Highly stable branched cationic polymer-functionalized black phosphorus electrochemical sensor for fast and direct ultratrace detection of copper ion

Copper ions (Cu2+) is an indispensable trace element in the process of metabolism and intake of excessive Cu2+ may lead to fatal diseases such as Alzheimer's disease. It is highly demanding to develop a sensitive, selective and convenient method for Cu2+ detection. In this work, thin-layer structured polyethyleneimine (PEI) decorated black phosphorus (BP) nanocomposite is one-step synthesized for an electrochemical sensor toward direct detection of Cu2+. This sensor achieves a wide detection range of 0.25–177 μM, a low detection limit of 0.02 μM much below the Environmental Protection Agency (EPA) maximum contaminant levels for drinking water (20 μM for Cu2+), and much faster response (1.5 s response time) and simpler operation than the conventional tedious anodic stripping voltammetry, ranking one of the best among all reported Cu2+ sensor. The great sensing enhancement is mainly due to a synergistic effect of BP and PEI of the composite, of which the former offers the reactivity while the latter splits the thick BP to thin-layer structured PEI-BP composite for larger reaction area. Meanwhile, a flexible sensor has been successfully fabricated and applied in detecting of Cu2+ in real samples of river, confirming the application feasibility of PEI-BP sensor in water environment control.

Machine Learning Models of Arsenic in Private Wells Throughout the Conterminous United States As a Tool for Exposure Assessment in Human Health Studies.

Arsenic from geologic sources is widespread in groundwater within the United States (U.S.). In several areas, groundwater arsenic concentrations exceed the U.S. Environmental Protection Agency maximum contaminant level of 10 μg per liter (μg/L). However, this standard applies only to public-supply drinking water and not to private-supply, which is not federally regulated and is rarely monitored. As a result, arsenic exposure from private wells is a potentially substantial, but largely hidden, public health concern. Machine learning models using boosted regression trees (BRT) and random forest classification (RFC) techniques were developed to estimate probabilities and concentration ranges of arsenic in private wells throughout the conterminous U.S. Three BRT models were fit separately to estimate the probability of private well arsenic concentrations exceeding 1, 5, or 10 μg/L whereas the RFC model estimates the most probable category (≤5, >5 to ≤10, or >10 μg/L). Overall, the models perform best at identifying areas with low concentrations of arsenic in private wells. The BRT 10 μg/L model estimates for testing data have an overall accuracy of 91.2%, sensitivity of 33.9%, and specificity of 98.2%. Influential variables identified across all models included average annual precipitation and soil geochemistry. Models were developed in collaboration with public health experts to support U.S.-based studies focused on health effects from arsenic exposure.

Co-exposure of sodium arsenite and uranyl acetate differentially alters gene expression in CD3/CD28 activated CD4+ T-cells.

Communities in the western region of the United States experience environmental exposure to metal mixtures from living in proximity to numerous unremediated abandoned uranium mines. Metals including arsenic and uranium co-occur in and around these sites at levels higher than the United States Environmental Protection Agency maximum contaminant levels. To address the potential effect of these metals on the activation of CD4+ T-cells, we used RNA sequencing methods to determine the effect of exposure to sodium arsenite (1 μM and 10 μM), uranyl acetate (3 μM and 30 μM) or a mixture of sodium arsenite and uranyl acetate (1 μM sodium arsenite + 3 μM uranyl acetate). Sodium arsenite induced a dose dependent effect on activation associated gene expression; targeting immune response genes at the lower dose. Increases in oxidative stress gene expression were observed with both sodium arsenite doses. While uranyl acetate alone did not significantly alter activation associated gene expression, the mixture of uranyl acetate with sodium arsenite demonstrated a combined effect relative to sodium arsenite alone. The results demonstrate the need to investigate metal and metalloid mixtures at environmentally relevant concentrations to better understand the toxicological impact of these mixtures on T-cell activation, function and immune dysregulation.

Reduction in drinking water arsenic exposure and health risk through arsenic treatment among private well households in Maine and New Jersey, USA

Over 2 million mostly rural Americans are at risk of drinking water from private wells that contain arsenic (As) exceeding the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL) of 10 micrograms per liter (μg/L). How well existing treatment technologies perform in real world situations, and to what extent they reduce health risks, are not well understood. This study evaluates the effectiveness of household As treatment systems in southern-central Maine (ME, n = 156) and northern New Jersey (NJ, n = 94) and ascertains how untreated well water chemistry and other factors influence As removal. Untreated and treated water samples, as well as a treatment questionnaire, were collected. Most ME households had point-of-use reverse-osmosis systems (POU RO), while in NJ, dual-tank point-of-entry (POE) whole house systems were popular. Arsenic treatment systems reduced well water arsenic concentrations ([As]) by up to two orders of magnitude, i.e. from a median of 71.7 to 0.8 μg/L and from a mean of 105 to 14.3 μg/L in ME, and from a median of 8.6 to 0.2 μg/L and a mean of 15.8 to 2.1 μg/L in NJ. More than half (53%) of the systems in ME reduced water [As] to below 1 μg/L, compared to 69% in NJ. The treatment system failure rates were 19% in ME (>USEPA MCL of 10 μg/L) and 16% in NJ (>NJ MCL of 5 μg/L). In both states, the higher the untreated well water [As] and the As(III)/As ratio, the higher the rate of treatment failure. POE systems failed less than POU systems, as did the treatment systems installed and maintained by vendors than those by homeowners. The 7-fold reduction of [As] in the treated water reduced skin cancer risk alone from 3765 to 514 in 1 million in ME, and from 568 to 75 in 1 million in NJ.

Multithiol functionalized graphene bio-sponge via photoinitiated thiol-ene click chemistry for efficient heavy metal ions adsorption

Heavy metals contamination in the natural waters remains an unresolved environmental challenge pressing for the development of purification technologies. This paper presents the green engineering of a new bio-sponge for heavy metals adsorption composed of alginate bio-polymeric network encapsulated with reduced graphene oxide (rGO) modified with iron oxide nanoparticles and covalently attached multithiol (pentaerythritol tetrakis-mercaptopropionate) molecules using photoinitiated thiol-ene click chemistry. The multithiol functionalized graphene bio-sponge (SH-Graphene bio-sponge) is designed to enhance adsorption performances of heavy metals including structural approach combined with oxygen functionalities and high density of sulfur-containing groups (10.2 at % S, confirmed by X-ray Photoelectron Spectroscopy, XPS) with high binding affinity towards specific heavy metals (Cd and Pb). It was shown that the level of thiol functionalization on the graphene structure within the bio-sponge can be controlled by tuning the Ultraviolet (UV) irradiation time without adjusting the concentration of the precursors. SH-functionalized graphene bio-sponge showed outstanding adsorption capacity for Pb (II): 101.01 mg/g and Cd (II): 102.99 mg/g, outperformed commercial and literature reported adsorbents in highly competitive selectivity studies using co-existing heavy metal ions (Cu, Co, Pb and Cd) spiked- sea water. The multithiol modified bio-sponge also showcased an excellent stability and reusability feature with only 0.015 mg/L Pb (II) detected, conforming the strict United States Environmental Protection Agency (US EPA) maximum contaminant level (MCL) for lead, after five recurring cycles using mixed heavy metal ions solution and acidic eluent. The outcomes from this work present valuable and promising contribution towards the development of a scalable and sustainable adsorbents for efficient remediation of heavy metals from waters.

Rapid and on-site simultaneous electrochemical detection of copper, lead and mercury in the Amazon river

In poor and remote zones of the world, such as the Amazon region, the lack of analytical infrastructures prevents regular quality assessments of water systems. The access to affordable, portable and robust analytical technologies for real-time and on-site water monitoring is, therefore, key to safeguard vulnerable communities and the environment. In this context, we have developed and successfully implemented an electrochemical methodology for the rapid (60 s) and effective simultaneous electrochemical detection of heavy metal ions of concern (Pb2+, Cu2+ and Hg2+) in water, with a single screen-printed electrode probe. In particular, we show a wide quantification range for each pollutant (5−300 μg L−1), and detection limits below the Environmental Protection Agency (EPA) maximum contaminant levels for drinking water: 0.015, 1.3 and 0.002 mg L−1 for Pb2+, Cu2+ and Hg2+, respectively. The electrochemical sensors were tested in high temperature and humidity conditions in remote areas of the Amazon river, highly affected by mining-related heavy metal pollution. The field measurements were validated against standard lab-based analytical methods, showing excellent agreement. Our methodology can lead to an affordable and portable diagnostic tool for rapid and on-site monitoring of heavy metals pollution in remote areas.

Engineering uranyl-chelating peptides from NikR for electrochemical peptide-based sensing applications

We have, for the first time, designed three uranyl-chelating peptides by modeling after the uranyl binding pocket found in a mutated Ni(II)-dependent transcriptional repressor (NikR). All three thiolated and methylene blue (MB)-modified peptides, NikR-5, NikR-11, and NikR-15, contain the five core amino acids responsible for target recognition, but the two longer peptides have either one or two additional glycine residues in between the five amino acids. These three peptide probes were then used in the fabrication of electrochemical peptide-based (E-PB) uranyl ion (U(VI)) sensors, with the goal of elucidating the effects of the added glycine residues and probe flexibility on target recognition. The sensing mechanism is similar to other “signal-off” E-PB sensors, in which binding of the target rigidifies the probe, resulting in a decrease in the redox signal from the tethered MB label. Although all three sensors responded to U(VI), the NikR-15 sensor's behavior was irreproducible and thus precluded from the rest of the study. The NikR-11 sensor showed the largest response to U(VI), whereas the NikR-5 sensor showed higher specificity for U(VI). The limit of detection was 50 nM for both sensors, which is well below the U.S. Environmental Protection Agency maximum contaminant level for uranium. Both sensors were further tested and proven functional in a 50% synthetic aquifer sample. Overall, the NikR-11 sensor, fabricated with the 11-amino acid probe, is deemed the optimal design. Incorporating glycine residues is a strategic way to lengthen the peptide slightly to improve target binding. This simple yet versatile approach to recreating binding pockets on electrode surfaces can potentially be employed in the design of other E-PB and surface-based metal ion sensors.

Metal(loid)s in Cucurbita pepo in a Uranium Mining Impacted Area in Northwestern New Mexico, USA.

More than 500 unreclaimed mines and associated waste sites exist on the Navajo Nation reservation as a result of uranium (U) mining from the 1940s through the 1980s. For this study, the impact of U-mine waste on a common, locally grown crop food was examined. The goal of this site-specific study was to determine metal(loid) concentration levels of arsenic (As), cadmium (Cd), cesium (Cs), molybdenum (Mo), lead (Pb), thorium (Th), U, vanadium (V) and selenium (Se) in Cucurbita pepo Linnaeus (squash), irrigation water, and soil using inductively coupled plasma-mass spectrometry. The concentrations of metal(loid)s were greatest in roots > leaves > edible fruit (p < 0.05), respectively. There were significant differences between metal(loid)s in squash crop plot usage (<5 years versus >30 years) for V (p = 0.001), As (p < 0.001), U (p = 0.002), Cs (p = 0.012), Th (p = 0.040), Mo (p = 0.047), and Cd (p = 0.042). Lead and Cd crop irrigation water concentrations exceeded the United States Environmental Protection Agency (USEPA) Maximum Contaminant Levels for drinking water for those metals. Edible squash concentration levels were 0.116 mg/kg of As, 0.248 mg/kg of Pb, 0.020 mg/kg of Cd, and 0.006 mg/kg of U. Calculated human ingestion of edible squash did not exceed Provisional Tolerable Weekly Intake or Tolerable Upper Limit levels from intake based solely on squash consumption. There does not appear to be a food-ingestion risk from metal(loid)s solely from consumption of squash. Safer access and emphasis on consuming regulated water was highlighted. Food intake recommendations were provided. Continued monitoring, surveillance, and further research are recommended.

Microencapsulated Photoluminescent Gold for ppb-Level Chromium(VI) Sensing.

Luminescent gold nanoclusters (Au NCs) are a promising probe material for selective chemical sensing. However, low luminescent intensity and an incomplete understanding of the mechanistic origin of the luminescence limit their practical implementation. We induced glutathione-capped Au NCs to aggregate within silica-coated microcapsular structures using polymer-salt aggregate self-assembly chemistry. The encapsulated NCs have a 5× luminescence enhancement compared to free Au NCs and can detect Cr(VI) at concentrations as low as 6 ppb (=0.12 μM CrO42-) through luminescence quenching, compared to free Au NCs, which have a limit of detection (LOD) of 52 ppb (=1 μM CrO42-). The LOD is 16× lower than the United States Environmental Protection Agency maximum contaminant level for total chromium (Cr(III) + Cr(VI), 100 ppb) in drinking water. No pH adjustment is needed using the encapsulated Au NCs, unlike the case for free Au NCs. The luminescent microcapsule material can sense Cr(VI) in simulated drinking water with a ∼20-30 ppb LOD, serving as a possible basis for a practical Cr(VI) sensor.

The MANAGE Drain Concentration database: A new tool compiling North American drainage nutrient concentrations

Artificially drained agricultural systems can be a primary contributor of non-point source nitrogen (N) and phosphorus (P) pollution to ground and surface waters; therefore, it is imperative to understand the mechanisms responsible for nutrient transport from this land use. Here, 79 drainage nutrient-related studies were used to compile 1564 site-years of agricultural drainage N and P concentrations (annual mean flow-weighted and annual arithmetic average) into a major database to aid in assessment of factors leading to nutrient loss through drainage systems. This new Drain Concentration table in the MANAGE (Measured Annual loads from AGricultural Environments) database is a publicly available resource (https://www.ars.usda.gov/plains-area/temple-tx/grassland-soil-and-water-research-laboratory/docs/manage-nutrient-loss-database). Probability of exceedance values were calculated using a Weibull distribution, and across the database, there was a 69% probability a drainage site-year would exceed an annual nitrate-N (NO3-N) concentration of 10 mg/L, the US Environmental Protection Agency Maximum Contaminant Level for drinking water, but only a 27% probability a reported site-year would exceed 0.0375 mg/L dissolved reactive phosphorus, which is a critical total P concentration to avoid freshwater eutrophication. While a surprising number of reported annual means were arithmetic averages rather than flow-weighted averages (27 vs. 71%), reporting of arithmetic means in peer-reviewed literature has decreased over time. We encourage further contributions to and analysis with the MANAGE database, so it can remain a resource for new efforts to better understand and mitigate nutrient losses from agricultural systems.

Developmental Toxicity of TCE Exposure in Zebrafish: Analyzing Vitamin D Metabolism

Background and Hypothesis: Trichloroethylene (TCE) is an industrial solvent used since the 1940s. A known carcinogen, it is found in over half of Superfund sites where levels have reached 12,000 parts per billion (ppb; µg/L), though the US Environmental Protection Agency maximum contaminant level in drinking water is 5 ppb. In this study, the zebrafish model was used to investigate the developmental toxicity of TCE by assessing its effects on metabolism. Preliminary studies have shown a reduction in gene expression of the cytochrome P450 (CYP) enzymes responsible for breakdown of vitamin D. As a result, we expected to see lower levels of downstream metabolites, namely calcitriol, as detected by an Enzyme-Linked Immunosorbent Assay (ELISA). &#x0D; Experimental Design: At 0-2 hours post fertilization (hpf), embryos were dosed with TCE at either 0 or 10 ppb. At 72 hpf, the larvae were removed from the TCE and prepared for the ELISA procedure. &#x0D; Results: ELISA revealed similar levels of calcitriol between the control and 10 ppb groups. The difference between the two groups did not show statistical significance (p&gt;0.05). &#x0D; Conclusion: These results suggest that there may not be a direct relationship between CYP gene expression and certain downstream metabolic effects or that the organism was able to compensate for the biological changes. If the latter, additional time points for TCE exposure could be evaluated. As studies continue, we plan to evaluate CYP gene expression at higher concentrations to correlate with other biological effects and determine if there is consistency with results from lower concentrations.

Natural clays with an inherent uranium component that nevertheless sequester uranium from contaminated water

Clays present a cost effective and sustainable method for removing uranium and heavy metals from drinking water because of their cation exchange capabilities. However, managing muddy suspensions is problematic; therefore, clay pellets as presented in this article are a promising alternative. Three standard clays and two regional clays were evaluated for sorption, both in powder form and in pellet structure for comparison. The objective was to evaluate individual sorption processes and assess the effect on uranium sorption due to the process of altering the clay powder to produce pellets. The sorption capacity of the pellets is sufficiently large to not only sorb the intrinsic non-bonded uranium but to continue to sorb uranium from contaminated water. Furthermore, the uranyl cation was also removed preferentially in the presence of Pb2+ and Cd2+ heavy metal cations, hydronium ions, and more importantly the naturally occurring cations, Na1+, Ca2+, and Mg2+ that occur in abundant concentrations. Clay pellets as well as powders reduced uranium concentrations, and in extreme cases from 450 ppb, 15 times the Environmental Protection Agency maximum contaminant level to non-detectable limits. Clay pellets are excellent candidates for the safe and manageable removal of uranium and heavy metals to produce potable water

Isotope Investigation of Nitrate in Soils and Agricultural Drains of the Lower Yakima Valley, Washington

Nitrate in the groundwater of the lower Yakima Valley, Washington frequently exceeds the Environmental Protection Agency (EPA) maximum contaminant level standard for potable water (10 mg/L), impacting communities with disadvantaged socioeconomic status. Nitrogen and oxygen isotopic signatures were determined for nitrate in soil leachates and irrigation return flow. Isotope signatures for nitrate from soil leachate had significant overlap with both the isotope signatures of naturally occurring soil nitrate at the nearby Hanford site, Washington and of groundwater nitrate attributed to manure and fertilizer application in a local EPA study. A mass balance calculation using Δ17O data suggests that there is a consistent ∼9% atmospheric contribution to nitrate in soil accumulations below caliche layers at several locations. This agrees with other research on the atmospheric contribution to naturally occurring soil nitrates in areas with similar mean annual precipitation values. We argue that this consistent ∼9% atmospheric component indicates that soil nitrate at depth is dominated by naturally occurring, biologically fixed nitrate across multiple sites. We suggest the flushing of naturally occurring soil nitrate to groundwater during land use conversion to irrigated agriculture may represent a previously overlooked significant nitrate input to aquifers in this region.

Guanidinium-Based Ionic Covalent Organic Framework for Rapid and Selective Removal of Toxic Cr(VI) Oxoanions from Water.

Ionic covalent organic frameworks make up an emerging class of functional materials in which the included ionic interfaces induce strong and attractive interactions with ionic species of the opposite charge. In this work, the strong and selective binding forces between the confined diiminoguanidinium groups in the framework and tetrahedral oxoanions have led to unparalleled effectiveness in the removal of the toxic chromium(VI) pollutant from aqueous solutions. The new functional framework can take up from 90 to 200 mg/g of chromium(VI), depending on the solution pH, and is capable of decreasing the chromium(VI) concentration in water from 1 ppm to 10 ppb within minutes (an order of magnitude below the current U.S. Environmental Protection Agency maximum contaminant level of 100 ppb), demonstrating superior properties among known ion exchange materials and natural sorbents.

Capacity Building through Water Quality and Safety Analyses in Herat, Afghanistan

Contaminated water is a leading cause of approximately 600 million annual cases of foodborne disease globally. Twenty percent of all child mortality in Afghanistan is attributed to diarrheal diseases. There are limited data on water quality and safety in Afghanistan as well as limited laboratory capacity for food and water analyses. The purpose of this study was to conduct a regional water assessment study and, in doing so, train the first class of food technology undergraduate students at Herat University (Herat City, Afghanistan) in basic water quality and safety laboratory techniques. In total, 235 water samples from private wells ( n = 128) and municipal water system taps ( n = 107) were collected from Herat Province, Afghanistan. Samples were aseptically collected, transferred, and analyzed at the Herat University Food Technology Laboratory for nitrate, nitrite, lead, phosphate, and arsenic concentrations; hardness; total coliforms; and Escherichia coli. We did not detect arsenic in any sample tested ( n = 234), and lead levels in samples tested ( n = 28) were below the U.S. Environmental Protection Agency maximum contaminant level (15 μg/L). In contrast, 38 of 232 samples had nitrate (NO3) levels greater than the maximum contaminant level (10 mg/L) and 15 of 232 samples had nitrite (NO2) levels > 0.3 mg/L. On average, well water was harder than municipal water; there were no differences in phosphate (PO4) levels. Furthermore, 93 (43.9%) of 212 samples had detectable coliforms (average CFU/100 mL) and 52 (24.3%) of 214 samples had detectable E. coli (average 28.6 CFU/100 mL). E. coli was detected in 21.4 and 26.7% of municipal and well water samples, respectively. This study indicates a clear need for systematic analyses of Herat City water to develop plans for water quality and safety improvement and management. The students engaged in the research project now have the basic research and analytical skills needed to address water and foodborne disease issues endemic in the area.