Water Supply Planning in the Face of Drought and Ecosystem Flows: Examining the Impact of the Bay-Delta Plan on Bay Area Water Supply.

In California, recent Bay-Delta Plan legislation attempts to balance water supply and ecosystem protection by requiring 40% of the flow to remain in-stream in the Tuolumne River from February through June. Serious questions remain about what this means for the Bay Area water supply, especially during drought. Our work develops a new approach to analyze how in-stream flow policy coupled with climate change could impact regional water supply over the coming decades. Results show that the new in-stream flow demand would exceed urban water deliveries in a typical year. In wet years, water supply performance is minimally impacted, but in drought, the policy can lead to less water in storage, delayed reservoir recovery, and increased time at critically low storage. Storage impact exceeding 50 000 acre-feet (60 million m3) is anticipated with at least 18% frequency, demonstrating that, climate uncertainty notwithstanding, this impact must be planned for and managed to ensure a reliable future water supply.

Metal toxin threat in wildland fires determined by geology and fire severity.

Accentuated by climate change, catastrophic wildfires are a growing, distributed global public health risk from inhalation of smoke and dust. Underrecognized, however, are the health threats arising from fire-altered toxic metals natural to soils and plants. Here, we demonstrate that high temperatures during California wildfires catalyzed widespread transformation of chromium to its carcinogenic form in soil and ash, as hexavalent chromium, particularly in areas with metal-rich geologies (e.g., serpentinite). In wildfire ash, we observed dangerous levels (327-13,100 µg kg-1) of reactive hexavalent chromium in wind-dispersible particulates. Relatively dry post-fire weather contributed to the persistence of elevated hexavalent chromium in surficial soil layers for up to ten months post-fire. The geographic distribution of metal-rich soils and fire incidents illustrate the broad global threat of wildfire smoke- and dust-born metals to populations. Our findings provide new insights into why wildfire smoke exposure appears to be more hazardous to humans than pollution from other sources.

Consider the Anoxic Microsite: Acknowledging and Appreciating Spatiotemporal Redox Heterogeneity in Soils and Sediments.

Reduction-oxidation (redox) reactions underlie essentially all biogeochemical cycles. Like most soil properties and processes, redox is spatiotemporally heterogeneous. However, unlike other soil features, redox heterogeneity has yet to be incorporated into mainstream conceptualizations of soil biogeochemistry. Anoxic microsites, the defining feature of redox heterogeneity in bulk oxic soils and sediments, are zones of oxygen depletion in otherwise oxic environments. In this review, we suggest that anoxic microsites represent a critical component of soil function and that appreciating anoxic microsites promises to advance our understanding of soil and sediment biogeochemistry. In sections 1 and 2, we define anoxic microsites and highlight their dynamic properties, specifically anoxic microsite distribution, redox gradient magnitude, and temporality. In section 3, we describe the influence of anoxic microsites on several key elemental cycles, organic carbon, nitrogen, iron, manganese, and sulfur. In section 4, we evaluate methods for identifying and characterizing anoxic microsites, and in section 5, we highlight past and current approaches to modeling anoxic microsites. Finally, in section 6, we suggest steps for incorporating anoxic microsites and redox heterogeneities more broadly into our understanding of soils and sediments.

Quantitative Separation of Unknown Organic-Metal Complexes by Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry.

Dissolved organic matter (DOM) is widely recognized to control the solubility and reactivity of trace metals in the environment. However, the mechanisms that govern metal-DOM complexation remain elusive, primarily due to the analytical challenge of fractionating and quantifying metal-organic species within the complex mixture of organic compounds that comprise DOM. Here, we describe a quantitative method for fractionation and element-specific detection of organic-metal complexes using liquid chromatography with online inductively coupled plasma mass spectrometry (LC-ICP-MS). The method implements a post-column compensation gradient to stabilize ICP-MS elemental response across the LC solvent gradient, thereby overcoming a major barrier to achieving quantitative accuracy with LC-ICP-MS. With external calibration and internal standard correction, the method yields concentrations of organic-metal complexes that were consistently within 6% of their true values, regardless of the complex's elution time. We used the method to evaluate the effects of four stationary phases (C18, phenyl, amide, and pentafluoroylphenyl propyl) on the recovery and separation of environmentally relevant trace metals (Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in Suwannee River Fulvic Acid and Suwannee River Natural Organic Matter. The C18, amide, and phenyl phases generally yielded optimal metal recoveries (>75% for all metals except Pb), with the phenyl phase separating polar species to a greater extent than C18 or amide. We also fractionated organic-bound Fe, Cu, and Ni in oxidized and reduced soils, revealing divergent metal-DOM speciation across soil redox environments. By enabling quantitative fractionation of DOM-bound metals, our method offers a means for advancing a mechanistic understanding of metal-organic complexation throughout the environment.

Uranium surface processes with sandstone and volcanic rocks in acidic and alkaline solutions.

Understanding the behaviour of uranium waste, for disposal purposes, is crucial due to the correlation between pH values and the disposal of distinct types of waste, with low level waste typically associated with acidic pH values, and higher and intermediate level waste commonly related to alkaline pH values. We studied the adsorption of U(VI) on sandstone and volcanic rock surfaces at pH 5.5 and 11.5 in aqueous solutions with and without bicarbonate (2 mM HCO3-) using XAS and FTIR. In the sandstone system, U(VI) adsorbs as a bidentate complex to Si at pH 5.5 without bicarbonate and as uranyl carbonate species with bicarbonate. At pH 11.5 without bicarbonate, U(VI) adsorbs as monodentate complexes to Si and precipitates as uranophane. With bicarbonate at pH 11.5, U(VI) precipitated as a Na-clarkeite mineral or remained as a uranyl carbonate surface species. In the volcanic rock system, U(VI) adsorbed to Si as an outer sphere complex at pH 5.5, regardless of the presence of bicarbonate. At pH 11.5 without bicarbonate, U(VI) adsorbed as a monodentate complex to one Si atom and precipitated as a Na-clarkeite mineral. With bicarbonate at pH 11.5, U(VI) sorbed as a bidentate carbonate complex to one Si atom. These results provide insight into the behaviour of U(VI) in heterogeneous, real-world systems related to the disposal of radioactive waste.

Seasonal Oxygenation of Contaminated Floodplain Soil Releases Zn to Porewater.

Soil zinc contamination is a major threat to water quality and sensitive ecosystems. While Zn itself is not redox-active in soils, transitions in soil redox conditions may promote mobilization of Zn from common Zn hosts, including Mn(IV)/Fe(III)-(hydr)oxides and sulfide precipitates, leading to elevated concentrations of dissolved Zn in surface and groundwater and thus a potential increase in Zn transport and uptake. Here, we examined the impacts of hydrologic fluctuations and coupled redox transitions on Zn partitioning in contaminated riparian soil in a mountain watershed. We found that oxygenation of the soil profile during low water conditions caused a spike in porewater Zn concentrations, driven by oxidative dissolution of amorphous ZnS and weak partitioning of Zn to Fe(III)-(hydr)oxides, hydroxy-interlayer vermiculite, and vermiculite. In contrast to Pb, released Zn did not immediately adsorb to Fe(III)-(hydr)oxides or particulate organic matter due to less-favorable sorption of Zn than that of Pb and, further, decreased Zn sorption at slightly acidic pH. As aridification intensifies and groundwater levels decline throughout the western United States, contaminated floodplain soils in mountain watersheds may be frequently oxygenated, leading to increased mobilization of dissolved Zn, which will amplify the threat Zn poses to water quality and ecosystem health.

Iron Reduction in Profundal Sediments of Ultraoligotrophic Lake Tahoe under Oxygen-Limited Conditions.

Increased periods of bottom water anoxia in deep temperate lakes due to decreasing frequency and depth of water column mixing in a warming climate may result in the reductive dissolution of iron minerals and increased flux of nutrients from the sediment into the water column. Here, we assessed the sediment properties and reactivities under depleted oxygen concentrations of Lake Tahoe, a deep ultraoligotrophic lake in the Sierra Nevada mountain range. Using whole-core incubation experiments, we found that a decrease in dissolved oxygen concentration in the top 2 cm of the sediment resulted in an extension of the microbial iron reduction zone from below 4.5 to below 1.5 cm depth. Concentrations of reactive iron generally decreased with sediment depth, and microbial iron reduction seemingly ceased as concentrations of Fe(II) approximated concentrations of reactive iron. These findings suggest that microorganisms preferentially utilized reactive iron and/or iron minerals became less reactive due to mineral transformation and surface passivation. The estimated release of iron mineral-associated phosphorus is not expected to change Lake Tahoe's trophic state but will likely contribute to increased phytoplankton productivity if mixed into surface waters.

Redox Properties of Solid Phase Electron Acceptors Affect Anaerobic Microbial Respiration under Oxygen-Limited Conditions in Floodplain Soils.

Mountain floodplain soils often show spatiotemporal variations in redox conditions that arise due to changing hydrology and resulting biogeochemistry. Under oxygen-depleted conditions, solid phase terminal electron acceptors (TEAs) can be used in anaerobic respiration. However, it remains unclear to what degree the redox properties of solid phases limit respiration rates and hence organic matter degradation. Here, we assess such limitations in soils collected across a gradient in native redox states from the Slate River floodplain (Colorado, U.S.A.). We incubated soils under anoxic conditions and quantified CO2 production and microbial Fe(III) reduction, the main microbial metabolic pathway, as well as the reactivity of whole-soil solid phase TEAs toward mediated electrochemical reduction. Fe(III) reduction occurred together with CO2 production in native oxic soils, while neither Fe(II) nor CO2 production was observed in native anoxic soils. Initial CO2 production rates increased with increasing TEA redox reactivity toward mediated electrochemical reduction across all soil depths. Low TEA redox reactivity appears to be caused by elevated Fe(II) concentrations rather than crystallinity of Fe(III) phases. Our findings illustrate that the buildup of Fe(II) in systems with long residence times limits the thermodynamic viability of dissimilatory Fe(III) reduction and thereby limits the mineralization of organic carbon.

Assessing Analytical Methods for the Rapid Detection of Lead Adulteration in the Global Spice Market.

Lead adulteration of spices, primarily via Pb chromate compounds, has been documented globally as a growing public health concern. Currently, Pb detection in spices relies primarily on expensive and time-consuming laboratory analyses. Advancing rapid Pb detection methods, inclusive of their accuracy and precision, would improve field assessments by food safety inspectors, stakeholders, and the public in the hope of reducing Pb exposure risks at its source. Here, we present two field procedures for Pb detection: portable X-ray fluorescence analysis (pXRF) and a simple colorimetric test. We assess their efficacy to detect Pb and its chemical form in seven spice types, including powders, spice-salt mixtures, and dried roots, compared to the proven laboratory technique, inductively coupled plasma mass spectrometry (ICP-MS). Lead concentrations measured using pXRF and ICP-MS were within 5% of each other for spice powders and 24% for dried roots. By pXRF, spice samples were analyzed within collection plastic bags without preparation, resulting in a detection limit of 2 mg Pb/kg for spice powders, which is comparable to national food standards. The colorimetric test utilized here targets hexavalent chromium, making the method selective to Pb chromate adulteration assuming that this is its dominant source in spices. Color development, and thus detection, was observed when Pb concentrations exceeded approximately 5-70 mg/kg in dried turmeric roots and 1000 mg/kg in spice powders; however, it was ineffective for the spice-salt mixture. We show that pXRF analysis and a colorimetric assay provide information that may improve field decisions about Pb adulteration in a range of spice types, helping to minimize Pb exposure.

Beaver dams overshadow climate extremes in controlling riparian hydrology and water quality.

Hydrologic extremes dominate chemical exports from riparian zones and dictate water quality in major river systems. Yet, changes in land use and ecosystem services alongside growing climate variability are altering hydrologic extremes and their coupled impacts on riverine water quality. In the western U.S., warming temperatures and intensified aridification are increasingly paired with the expanding range of the American beaver-and their dams, which transform hydrologic and biogeochemical cycles in riparian systems. Here, we show that beaver dams overshadow climatic hydrologic extremes in their effects on water residence time and oxygen and nitrogen fluxes in the riparian subsurface. In a mountainous watershed in Colorado, U.S.A., we find that the increase in riparian hydraulic gradients imposed by a beaver dam is 10.7-13.3 times greater than seasonal hydrologic extremes. The massive hydraulic gradient increases hyporheic nitrate removal by 44.2% relative to seasonal extremes alone. A drier, hotter climate in the western U.S. will further expand the range of beavers and magnify their impacts on watershed hydrology and biogeochemistry, illustrating that ecosystem feedbacks to climate change will alter water quality in river systems.

Nitrate Controls on the Extent and Type of Metal Retention in Fine-Grained Sediments of a Simulated Aquifer.

Aquifer groundwater quality is largely controlled by sediment composition and physical heterogeneity, which commonly sustains a unique redox gradient pattern. Attenuation of heavy metals within these heterogeneous aquifers is reliant on multiple factors, including redox conditions and redox-active species that can further influence biogeochemical cycling. Here, we simulated an alluvial aquifer system using columns filled with natural coarse-grained sediments and two domains of fine-grained sediment lenses. Our goal was to examine heavy metal (Ni and Zn) attenuation within a complex aquifer network and further explore nitrate-rich groundwater conditions. The fine-grained sediment lenses sustained reducing conditions and served as a sink for Ni sequestration─in the form of Ni-silicates, Ni-organic matter, and a dominant Ni-sulfide phase. The silicate clay and sulfide pools were also important retention mechanisms for Zn; however, Ni was associated more extensively with organic matter compared to Zn, which formed layered double hydroxides. Nitrate-rich conditions promoted denitrification within the lenses that was coupled to the oxidation of Fe(II) and the concomitant precipitation of an Fe(III) phase with higher structural distortion. A decreased metal sulfide pool also resulted, where nitrate-rich conditions generated an average 20% decrease in solid-phase Ni, Zn, and Fe. Ultimately, nitrate plays a significant role in the aquifer's biogeochemical cycling and the capacity to retain heavy metals.

Mechanism of Arsenic Partitioning During Sulfidation of As-Sorbed Ferrihydrite Nanoparticles.

Knowledge of how arsenic (As) partitions among various phases in Fe-rich sulfidic environments is critical for understanding the fate and mobility of As in such environments. We studied the reaction of arsenite and arsenate sorbed on ferrihydrite nanoparticle surfaces with dissolved sulfide at varying S/Fe ratios (0.1-2.0) to understand the fate and transformation mechanism of As during sulfidation of ferrihydrite. By using aqueous As speciation analysis by IC-ICP-MS and solid-phase As speciation analysis by synchrotron-based X-ray absorption spectroscopy (XAS), we were able to discern the mechanism and pathways of As partitioning and thio-arsenic species formation. Our results provide a mechanistic understanding of the fate and transformation of arsenic during the codiagenesis of As, Fe, and S in reducing environments. Our aqueous-phase As speciation data, combined with solid-phase speciation data, indicate that sulfidation of As-sorbed ferrihydrite nanoparticles results in their transformation to trithioarsenate and arsenite, independent of the initial arsenic species used. The nature and extent of transformation and the thioarsenate species formed were controlled by S/Fe ratios in our experiments. However, arsenate was reduced to arsenite before transformation to trithioarsenate.

Export of Organic Carbon from Reduced Fine-Grained Zones Governs Biogeochemical Reactivity in a Simulated Aquifer.

Sediment interfaces in alluvial aquifers have a disproportionately large influence on biogeochemical activity and, therefore, on groundwater quality. Previous work showed that exports from fine-grained, organic-rich zones sustain reducing conditions in downstream coarse-grained aquifers beyond the influence of reduced aqueous products alone. Here, we show that sustained anaerobic activity can be attributed to the export of organic carbon, including live microorganisms, from fine-grained zones. We used a dual-domain column system with ferrihydrite-coated sand and embedded reduced, fine-grained lenses from Slate River (Crested Butte, CO) and Wind River (Riverton, WY) floodplains. After 50 d of groundwater flow, 8.8 ± 0.7% and 14.8 ± 3.1% of the total organic carbon exported from the Slate and Wind River lenses, respectively, had accumulated in the sand downstream. Furthermore, higher concentrations of dissolved Fe(II) and lower concentrations of dissolved organic carbon in the sand compared to total aqueous transport from the lenses suggest that Fe(II) was produced in situ by microbial oxidation of organic carbon coupled to iron reduction. This was further supported by an elevated abundance of 16S rRNA and iron-reducing (gltA) gene copies. These findings suggest that organic carbon transport across interfaces contributes to downstream biogeochemical reactions in natural alluvial aquifers.

Human health risk assessment and geochemical mobility of rare earth elements in Amazon soils.

Rare earth elements (REEs) are a grouping of elements that encompasses lanthanides, yttrium and scandium due to their similar chemical properties and occurrence in ore deposits. Over the past few decades, economic interest in REEs has increased due to their use in several types of industries such as high-tech, medicine and agriculture. Extraction of REEs has been followed, in general, by incorrect disposal of tailing and waste, creating hazardous conditions in several countries. However, the magnitude of the possible impacts on ecosystem and human health are relatively unknown, especially in tropical systems. Thus, the objectives of this study were to assess the geochemical mobility and the bioaccessibility of REEs based on a series of chemical extractions and in vitro essay. We also tested two promising simple protocols (0.01 mol L-1 CaCl2 and 0.43 mol L-1 HNO3) for measuring REE bioaccessible fractions through a single extraction. Our findings show that the bioavailable fractions represent less than 20% of the ΣREEs fraction in all soil samples examine. Similarly, the oral bioaccessibility obtained by two in vitro methods (Gastric protocol and Gastric-Intestinal protocol) and by the single extraction tests represented less than 20% of the ΣREE contents. The non-carcinogenic risks and the carcinogenic risks associated to REEs oral exposure were low for children and adults. The extractions with 0.01 mol L-1 CaCl2 showed great potential as a method for measuring the REEs bioaccessible fraction.

Bone manganese is a sensitive biomarker of ongoing elevated manganese exposure, but does not accumulate across the lifespan.

Studies have established associations between environmental and occupational manganese (Mn) exposure and executive and motor function deficits in children, adolescents, and adults. These health risks from elevated Mn exposure underscore the need for effective exposure biomarkers to improve exposure classification and help detect/diagnose Mn-related impairments. Here, neonate rats were orally exposed to 0, 25, or 50 mg Mn/kg/day during early life (PND 1-21) or lifelong through âˆ¼ PND 500 to determine the relationship between oral Mn exposure and blood, brain, and bone Mn levels over the lifespan, whether Mn accumulates in bone, and whether elevated bone Mn altered the local atomic and mineral structure of bone, or its biomechanical properties. Additionally, we assessed levels of bone Mn compared to bone lead (Pb) in aged humans (age 41-91) living in regions impacted by historic industrial ferromanganese activity. The animal studies show that blood, brain, and bone Mn levels naturally decrease across the lifespan without elevated Mn exposure. With elevated exposure, bone Mn levels were strongly associated with blood Mn levels, bone Mn was more sensitive to elevated exposures than blood or brain Mn, and Mn did not accumulate with lifelong elevated exposure. Elevated early life Mn exposure caused some changes in bone mineral properties, including altered local atomic structure of hydroxyapatite, along with some biomechanical changes in bone stiffness in weanlings or young adult animals. In aged humans, blood Mn ranged from 5.4 to 23.5 ng/mL; bone Mn was universally low, and decreased with age, but did not vary based on sex or female parity history. Unlike Pb, bone Mn showed no evidence of accumulation over the lifespan, and may not be a biomarker of cumulative long-term exposure. Thus, bone may be a useful biomarker of recent ongoing Mn exposure in humans, and may be a relatively minor target of elevated exposure.

Nitrate in Drinking Water during Pregnancy and Spontaneous Preterm Birth: A Retrospective Within-Mother Analysis in California.

BACKGROUND: Nitrate is a widespread groundwater contaminant and a leading cause of drinking water quality violations in California. Associations between nitrate exposure and select adverse birth outcomes have been suggested, but few studies have examined gestational exposures to nitrate and risk of preterm birth (before 37 wk gestation). OBJECTIVE: We investigated the association between elevated nitrate in drinking water and spontaneous preterm birth through a within-mother retrospective cohort study of births in California. METHODS: We acquired over 6 million birth certificate records linked with Office of Statewide Health Planning and Development hospital discharge data for California births from 2000-2011. We used public water system monitoring records to estimate nitrate concentrations in drinking water for each woman's residence during gestation. After exclusions, we constructed a sample of 1,443,318 consecutive sibling births in order to conduct a within-mother analysis. We used separate conditional logistic regression models to estimate the odds of preterm birth at 20-31 and 32-36 wk, respectively, among women whose nitrate exposure changed between consecutive pregnancies. RESULTS: Spontaneous preterm birth at 20-31 wk was increased in association with tap water nitrate concentrations during pregnancy of 5 to <10mg/L [odds ratio (OR)=1.47; 95% confidence interval (CI): 1.29, 1.67] and ≥10mg/L (OR=2.52; 95% CI: 1.49, 4.26) compared with <5mg/L (as nitrogen). Corresponding estimates for spontaneous preterm birth at 32-36 wk were positive but close to the null for 5 to <10mg/L nitrate (OR=1.08; 95% CI: 1.02, 1.15) and for ≥10mg/L nitrate (OR=1.05; 95% CI: 0.85, 1.31) vs. <5mg/L nitrate. Our findings were similar in several secondary and sensitivity analyses, including in a conventional individual-level design. DISCUSSION: The results suggest that nitrate in drinking water is associated with increased odds of spontaneous preterm birth. Notably, we estimated modestly increased odds associated with tap water nitrate concentrations of 5 to <10mg/L (below the federal drinking water standard of 10mg/L) relative to <5mg/L. https://doi.org/10.1289/EHP8205.

The effect of porewater ionic composition on arsenate adsorption to clay minerals.

Adsorption of arsenate on clay minerals can control the partitioning and mobility of arsenic and subsequent contamination of groundwater. While the effect of ionic strength on arsenic adsorption to phyllosilicate minerals has been evaluated for various clay minerals, the specific ionic composition of the surrounding porewater can play a critical role in promoting adsorption (or desorption) of arsenate (HxAsO4x-4). We conducted a series of adsorption isotherms to evaluate the adsorption of arsenate to various phyllosilicates in the presence of monovalent (K+), divalent (Mg2+, Ca2+), and trivalent (La3+) cations while maintaining constant ionic strength and pH. Adsorption isotherms were combined with surface complexation modeling to examine retention processes of arsenate as a function of ionic composition in the surrounding solution. The higher charge density of greater valent cations results in stronger outer-sphere bridging complexes between negatively charged phyllosilicate mineral surfaces and negatively charged arsenate oxyanions. Higher valent cations thus enhance the propensity for arsenate adsorption on phyllosilicate minerals. We further deciphered surface complexation processes by conducting adsorption isotherms on various clay minerals including smectite, illite, and pyrophyllite to evaluate the role of interlayer, permanent charge, and terminal edge sites. We conclude that arsenate is most likely retained largely on the planar surface where structural negative charge emanates allowing cation bridging complexes to develop. Our findings illustrate that clay mineralogy of soils and sediments can combine with porewater ionic composition (and specifically the proportion of divalent cations) to describe arsenic transport, particularly in iron- or aluminum-oxide poor systems.

Porewater Lead Concentrations Limited by Particulate Organic Matter Coupled With Ephemeral Iron(III) and Sulfide Phases during Redox Cycles Within Contaminated Floodplain Soils.

Lead contamination in soils and sediments is a major threat to water quality. In surface and near-surface environments, Pb is not redox active; however, common Pb hosts, including Fe(III)-(hydr)oxides and sulfides, dissolve and precipitate as redox conditions change. Dissolution of Pb hosts may release Pb to porewater, leading to spikes in dissolved Pb concentrations and potential transport into surface or groundwater. Here, we examine the impacts of hydrologically coupled redox transitions on Pb partitioning in contaminated floodplain soils. We find that the affinity of Pb for particulate organic matter (POM), inclusive of mineral-associated organic matter, ensures that across redox transitions Pb is retained in the solid phase, despite host-phase (Fe(III)-(hydr)oxide and sulfide) dissolution. As seasonal hydrologic dynamics shift porewater redox conditions, Pb-bearing Fe(III)-(hydr)oxides (Pb-HFO) and sulfides (PbS) are dissolved and (re)precipitated. However, despite these shifts in redox conditions and associated host-phase transformations, Pb retention on POM, coupled with the formation of PbS and Pb-HFO, maintains dissolved Pb concentrations below 17 µg L-1. Importantly, the predominance of Pb adsorbed on POM alongside low dissolved Pb concentrations indicates that Pb released from HFO and PbS is retained by POM. Thus, despite host-phase dissolution during redox transitions, partitioning of Pb to the aqueous phase is minimal and, therefore, transport of dissolved Pb is unlikely.

Effects of moisture and physical disturbance on pore-scale oxygen content and anaerobic metabolisms in upland soils.

Soils are the largest dynamic stock of carbon (C) on Earth, and microbial respiration of soil organic C accounts for over 25% of global carbon dioxide (CO2) emissions. Zones of oxygen depletion in upland soils (anaerobic microsites) are increasingly recognized as an important control on soil microbial respiration rates, but the factors governing the volume and distribution of anaerobic microsites are relatively unknown. We measured the dissolved oxygen (DO) content of porewater from incubated soil cores of varying moisture contents (<80% and >80% water saturation) and degrees of disturbance (undisturbed, conventionally tilled, and physically disturbed). Porewater was extracted sequentially from pores constrained by three effective pore diameters, ≥3.0 µm, 3.0-1.0 µm, and 1.0-0.6 µm, from cores incubated for 7, 14, or 28 days, using a modified Tempe cell extraction system. We observed a parabolic pattern in mean dissolved oxygen (DO) concentrations across pore sizes, independent of soil moisture and degree of disturbance. Specifically, DO values within the largest and smallest pore domains were relatively depleted (155 ± 10 µM and 160 ± 11 µM, respectively), while DO values within medium pores were closer to saturation (214 ± 8 µM). The observed DO pattern provides insight into the balance of microbial oxygen demand versus oxygen supply across pore domains within upland soils. Additionally, we observed iron and manganese reduction in all soils except samples subjected to disturbance and incubated at <80% water saturation, suggesting that disturbance enhances aeration and diminishes anaerobic metabolisms within upland soils. Our findings highlight the influence of soil moisture and management on soil redox and CO2 efflux rates.

Geochemical signatures and natural background values of rare earth elements in soils of Brazilian Amazon.

Rare earth elements (REEs) are generally defined as a homogenous group of elements with similar physical-chemical properties, encompassing Y and Sc and the lanthanides elements series. Natural REEs contents in soils depend on the parent material, the soil genesis processes and can be gradually added to the soil by anthropogenic activities. The REEs have been considered emerging pollutants in several countries, so the establishment of regulatory guidelines is necessary to avoid environmental contamination. In Brazil, REE soils data are restricted to some regions, and knowledge about them in the Amazon soils is scarce, although this biome covers more than 40% of the Brazilian territory. Thus, the objectives of this study were to determine the REE content in soils of two hydrographic basins (Solimões and Rio Negro) of the Amazon biome, establish their Quality Reference Values (QRV) and to investigate the existence of enrichment of REEs in urban soils. The ΣREE(Y + Sc) content of Solimões surface samples was 109.28 mg kg-1 and the ΣREE(Y + Sc) content in the subsurface samples was 94.11 mg kg-1. In soils of Rio Negro basin, the ΣREE(Y + Sc) was 43.95 15 mg kg-1 surface samples and 38.40 mg kg-1 in subsurface samples. The ΣREE(Y + Sc) in urban topsoils samples was 38.62 mg kg-1. The REEs contents pattern in three studied areas are influenced in different amplitude by natural soil properties. The REEs content in urban topsoils were slightly higher than the Rio Negro pristine soils, but the ecological risk was low. QRVs recommend for Solimões soils ranged from 0.01 (Lu) to 145.6 mg kg-1 (Ce) and for Rio Negro soils ranged from 0.05 (Lu) to 15.8 mg kg-1 (Ce).