Differential Effects of Arsenic in Drinking Water on Mouse Hepatic and Intestinal Heme Oxygenase-1 Expression.

Arsenic exposure has been associated with the risks of various diseases, including cancers and metabolic diseases. The aim of this study was to examine the effects of arsenic exposure via drinking water on the expression of heme oxygenase-1 (HO-1), a major responsive gene to arsenic-induced oxidative stress, in mouse intestinal epithelial cells which is the first site of exposure for ingested arsenic, and the liver, a known target of arsenic toxicity. The expression of HO-1 was determined at mRNA, protein, or enzymic activity levels in mice exposed to sodium arsenite through drinking water, at various doses (0, 2.5, 10, 25, 100 ppm), and for various time periods (1, 3, 7, or 28 days). HO-1 was significantly induced in the intestine, but not liver, at arsenic doses of 25 ppm or lower. The intestinal HO-1 induction was seen in both males and females, plateaued within 1-3 days of exposure, and was accompanied by increases in microsomal HO activity. In mice exposed to 25-ppm of arsenite for 7 days, total arsenic and As(III) levels in intestinal epithelial cells were significantly higher than in the liver. These findings identify intestinal epithelial cells as likely preferential targets for arsenic toxicity and support further studies on the functional consequences of intestinal HO-1 induction.

Lung-Based, Exosome Inhibition Mediates Systemic Impacts Following Particulate Matter Exposure.

Particulate matter (PM) exposure is a global health issue that impacts both urban and rural communities. Residential communities in the Southwestern United States have expressed concerns regarding the health impacts of fugitive PM from rural, legacy mine-sites. In addition, the recent literature suggests that exosomes may play a role in driving toxicological phenotypes following inhaled exposures. In this study, we assessed exosome-driven mechanisms and systemic health impacts following inhaled dust exposure, using a rodent model. Using an exosome inhibitor, GW4869 (10 µM), we inhibited exosome generation in the lungs of mice via oropharyngeal aspiration. We then exposed mice to previously characterized inhaled particulate matter (PM) from a legacy mine-site and subsequently assessed downstream behavioral, cellular, and molecular biomarkers in lung, serum, and brain tissue. Results indicated that CCL-2 was significantly upregulated in the lung tissue and downregulated in the brain (p < 0.05) following PM exposure. Additional experiments revealed cerebrovascular barrier integrity deficits and increased glial fibrillary acidic protein (GFAP) staining in the mine-PM exposure group, mechanistically dependent on exosome inhibition. An increased stress and anxiety response, based on the open-field test, was noted in the mine-PM exposure group, and subsequently mitigated with GW4869 intervention. Exosome lipidomics revealed 240 and eight significantly altered positive-ion lipids and negative-ion lipids, respectively, across the three treatment groups. Generally, phosphatidylethanolamine (PE) and phosphatidylcholine (PC) lipids were significantly downregulated in the PM group, compared to FA. In conclusion, these data suggest that systemic, toxic impacts of inhaled PM may be mechanistically dependent on lung-derived, circulating exosomes, thereby driving a systemic, proinflammatory phenotype.

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.

Association between the polymorphism of three genes involved in the methylation and efflux of arsenic (As3MT, MRP1, and P-gp) with lung cancer in a Mexican cohort.

Lung cancer is the most common neoplasm and the primary cause-related mortality in developed and in most of nondeveloped countries. Epidemiological studies have demonstrated that even at low arsenic doses, the lungs are one of the main target organs and that chronic arsenic exposure has been associated with an increase in lung cancer development. Among the risk factors for cancer, arsenic methylation efficiency (As3MT) and the clearance of arsenic from cells by two members of the ATP-binding cassette (ABC) transporter family (multidrug resistance protein 1 [MRP1] and P-glycoprotein [P-gp]) play an important role in processing of arsenic and decreasing its intracellular levels. This study aimed to evaluate the association between chronic exposure to arsenic with polymorphism of three proteins involved in arsenic metabolism and efflux of the metalloid in subjects with lung cancer. Polymorphism in As3MT, MRP1, and P-gp modified the arsenic metabolism increasing significantly the AsV urinary levels. A significant association between MRP1 polymorphisms with an increase in the risk for cancer was found. The high inorganic arsenic urinary levels registered in the studied subjects suggest a reduction in the efficiency of As3MT, MRP1, and P-gp firstly because of gene polymorphisms and secondarily because of high internal inorganic arsenic levels. MRP1 polymorphism was associated with a twofold increase in the risk of lung cancer.

Assessment of YAP gene polymorphisms and arsenic interaction in Mexican women with breast cancer.

The identification of gene-environment interactions related to breast cancer reveals the biological and molecular mechanisms underlying the disease and allows the distinction of women at high risk from women at lower risk, which could decrease the morbimortality of this neoplasm. The current study evaluated the association between polymorphisms rs1820453 and rs11225161 of the Yes-associated protein (YAP) gene in women with breast cancer exposed to arsenic (As) through drinking water. In total, 182 women were assessed for the frequency of YAP rs1820453 and rs11225161 polymorphisms and As urinary levels. The results demonstrated a positive and significant association between breast cancer and smoking, type of drinking water, and levels of AsIII , AsV and inorganic As (iAs) but not the YAP gene polymorphisms evaluated. In conclusion, our data showed that the source of drinking water and AsV and iAs urinary levels increased the risk for breast cancer, but no interactions between YAP gene polymorphisms and As urinary levels were found.

Rare earth elements (REY) sorption on soils of contrasting mineralogy and texture.

Rare earth elements (REY) are the lanthanide elements (Z = 57-71), which have an ever-growing occurrence in present-day industries, agriculture, and modern life. Consequently, environmental concentrations are expected to increase accordingly as a result of intensified utilization. Soils are an important sink for REY, yet little research has been conducted concerning activity, inputs, and lability in soil systems. This study evaluated the REY (lanthanides + yttrium) sorption and partition coefficients (Kd) in two broadly representative natural soils (A horizon), with contrasting mineralogy and organic character, formed under distinct environmental conditions: an Oxisol from Brazil and a Mollisol from the USA. Batch reactions of soils suspended in a background electrolyte solution of 5 µmoles kg-1 of Ca(NO3)2 at 1:100 solid to solution were reacted with 80 µmoles kg-1 REY added individually and in multi-REY competitive systems to evaluated adsorption after 3 h and 72 h over a wide pH range (from ca. 2 to 8). Results showed sorption was similar for all REY within each soil type when examined at the natural measured soil pH; Mollisol pH 6.85, Oxisol pH 4.35. However, REY sorption (by Kd) was nearly two-fold greater in the Mollisol compared to the Oxisol for the single REY experiments. Multi-REY competitive sorption reactions showed a decrease in Kd for both soils at 3 and 72 h, and to a greater extent for the Mollisol, indicating soil type had a strong effect on the sorption affinity of each REY. It was also observed that REY sorption increased from low to high pH (pH 2-8) in the Oxisol, and increased with pH from 2 up to the point zero charge (PZC) in the Mollisol, then stabilized. The varying REY Kd values from these two distinct and abundant soils, with and without REY competition, and over a range of pH are explained in terms of soil mineralogy (i.e., 2:1 clays in the Mollisol; oxides in the Oxisol) and organic matter content. Our findings show that soil characteristic controls sorption, precipitation, and cation exchange capacity, which are the key mechanisms for predicting REY fate and transport in the environment.

Quantifying particulate and colloidal release of radionuclides in waste-weathered hanford sediments.

At the Hanford Site in the state of Washington, leakage of hyperalkaline, high ionic strength wastewater from underground storage tanks into the vadose zone has induced mineral transformations and changes in radionuclide speciation. Remediation of this wastewater will decrease the ionic strength of water infiltrating to the vadose zone and could affect the fate of the radionuclides. Although it was shown that radionuclide host phases are thermodynamically stable in the presence of waste fluids, a decrease in solution ionic strength and pH could alter aggregate stability and remobilize radionuclide-bearing colloids and particulate matter. We quantified the release of particulate, colloidal, and truly dissolved Sr, Cs, and I from hyperalkaline-weathered Hanford sediments during a low ionic strength pore water leach and characterized the released particles and colloids using electron microscopy and X-ray diffraction. Although most of the Sr, Cs, and I was released in dissolved form, between 3 and 30% of the Sr and 4 to 18% of the Cs was associated with a dominantly zeolitic mobile particulate fraction. Thus, the removal of hyperalkaline wastewater will likely induce Sr and Cs mobilization that will be augmented by particulate- and colloid-facilitated transport.

Response of key soil parameters during compost-assisted phytostabilization in extremely acidic tailings: effect of plant species.

Phytostabilization of mine tailings acts to mitigate both eolian dispersion and water erosion events which can disseminate barren tailings over large distances. This technology uses plants to establish a vegetative cover to permanently immobilize contaminants in the rooting zone, often requiring addition of an amendment to assist plant growth. Here we report the results of a greenhouse study that evaluated the ability of six native plant species to grow in extremely acidic (pH ∼ 2.5) metalliferous (As, Pb, Zn: 2000-3000 mg kg(-1)) mine tailings from Iron King Mine Humboldt Smelter Superfund site when amended with a range of compost concentrations. Results revealed that three of the six plant species tested (buffalo grass, mesquite, and catclaw acacia) are good candidates for phytostabilization at an optimum level of 15% compost (w/w) amendment showing good growth and minimal shoot accumulation of metal(loid)s. A fourth candidate, quailbush, also met all criteria except for exceeding the domestic animal toxicity limit for shoot accumulation of zinc. A key finding of this study was that the plant species that grew most successfully on these tailings significantly influenced key tailings parameters; direct correlations between plant biomass and both increased tailings pH and neutrophilic heterotrophic bacterial counts were observed. We also observed decreased iron oxidizer counts and decreased bioavailability of metal(loid)s mainly as a result of compost amendment. Taken together, these results suggest that the phytostabilization process reduced tailings toxicity as well as the potential for metal(loid) mobilization. This study provides practical information on plant and tailings characteristics that is critically needed for successful implementation of assisted phytostabilization on acidic, metalliferous mine tailings sites.

Solid-state NMR identification and quantification of newly formed aluminosilicate phases in weathered kaolinite systems.

The weathering of a specimen kaolinite clay was studied over the course of 369 d via solid-state 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and high-field 27Al MAS NMR. The chosen baseline solution conditions (0.05 mol kg-1 of Al, 2 mol kg-1 of Na+, 1 mol kg-1 of NO3-, 1 mol kg-1 of OH-, and pH approximately 13.8) approximate those of solutions leaking from waste tanks at the Hanford Site in Richland, WA. Nonradioactive Cs and Sr cations were added to this synthetic tank waste leachate (STWL) solution at concentrations of 10(-3), 10(-4), and 10(-5) molal (m) to represent their radionuclide counterparts. The transformations of silicon- and aluminum-containing solid phase species were monitored quantitatively by using NMR spectroscopy, with the resulting spectra directly reporting the influence of the initial Cs and Sr on formation and transformation of the neo-formed solids. At the lowest concentration of Cs and Sr employed (10(-5) m in each cation) peaks consistent with the formation of zeolite-like minerals were detected via 29Si and 27Al MAS NMR as early as 33 d. At concentrations of 10(-3) m in each cation, new silicon species are not detected until 93 d, although neophases containing four-coordinate aluminum were detectable at earlier reaction times via 27Al MAS NMR. At the highest magnetic field strengths employed in this NMR study, deconvolutions of resonances detected in the tetrahedral region of the 27Al MAS spectra yielded multiple components, indicating the existence of at least four new aluminum-containing phases. Two of these phases are identified as sodalite and cancrinite through comparison with diffuse-reflectance infrared (DRIFT) spectra and powder X-ray diffraction (XRD) results, while a third phase may correlate with a previously detected aluminum-rich chabazite phase. All measurable solid reaction products have been quantified via their 27Al MAS resonances acquired at high magnetic field strengths (17.6 T), and the quantitative nature of the 27Al NMR data shows that cancrinite growth increases while sodalite reaches a steady state with respect to total aluminum in the solid phases. The data also relate the coupling of Cs sorption to the ripening of feldspathoid phases in this heterogeneous system as a function of time, and illustrate the important influence of co-contaminants on the environmental reaction kinetics studied here.

Linking cesium and strontium uptake to kaolinite weathering in simulated tank waste leachate.

Weathering behavior of kaolinite was studied in batch systems under geochemical conditions characteristic of tank waste released to the vadose zone at the Hanford Site, WA (0.05 M Al(T), 2 M Na+, 1 M N03-, pH approximately 14, Cs+ and Sr2+ present as co-contaminants). Time series experiments were conducted from 0 to 369 d, with initial Cs+ and Sr2+ concentrations ranging from 10(-5) to 10(-3) M. Dissolution of kaolinite increased soluble Si and Al to maximum levels at 7 d (Cs and Sr concentrations of 10(-5) and 10(-4) M) or 33 d (Cs and Sr concentrations of 10(-3) M). Subsequent precipitation of Si and Al was coupled to the formation of oxalate-extractable solids that incorporated Cs and Sr. Strontium sorption was nearly complete within 24 h for initial Sr concentrations (Sr0) < or = 10(-4) whereas Cs uptake increased over the full year of the experiment for all initial Cs concentrations. Spectroscopic analyses revealed neoformed solids including the zeolite Na-Al silicate (Al-chabazite), and feldspathoids sodium aluminum nitrate silicate (NO3-sodalite), and sodium aluminum nitrate silicate hydrate (NO3-cancrinite), which can incorporate Cs. Single-pulse 27Al solid-state nuclear magnetic resonance (NMR) spectroscopyyielded first-order rate constants (k)for mineral transformation that decreased from 3.5 x 10(-3) to 2 x 10(-3) d(-1) as Cs and Sr concentrations were increased from 10(-5) to 10(-3) M. Discrete strontium silicate solids were also observed. The incongruent dissolution of kaolinite promoted the sequestration of contaminants into increasingly recalcitrant solid phases over the 1-yr time period.