Saltwater intrusion increases phosphorus abundance and alters availability in coastal soils with implications for future sea level rise.

Sea level rise (SLR) promotes saltwater intrusion (SWI) into coastal soils globally at an increasing rate, impacting phosphorus (P) dynamics and adjacent water quality. However, how SWI influences P molecular speciation and availability in coastal soils remains poorly understood. By using a space-for-time substitution strategy, we evaluated the SWI impacts on P transformation along a SWI gradient at the Rehoboth Inland Bay, which consists of five sampling locations along a transect representing different SWI degrees. Soils were analyzed at the macro- and micro-scale using X-ray absorption near edge spectroscopy (XANES) and the modified Hedley fractionation. With increasing distance from the Bay, soil salinity (29.3-0.07 mmhos cm-1), the proportion of Fe3+ to total Fe, and P concentrations decreased. The fractionation showed that recalcitrant P was dominant (86.9-89.5% of total P). With increasing SWI, labile P increased gradually, reached a plateau, and then decreased sharply. Bulk XANES spectroscopy showed that soil P was likely dominated by iron and aluminum-associated P (Fe/Al-P), regardless of the SWI degree. Hence, with increasing SWI, P increasingly accumulated in a recalcitrant pool, mainly as Fe/Al-P. µ-XANES spectroscopy revealed that calcium-associated P (Ca-P) existed in P-rich spots of the greatest SWI soil while Al-P occurred in P-rich spots of the low SWI soil, consistent with the greater HCl-P (presumably Ca-P) in the former soil. Overall, results demonstrate that SWI impacts P availability and environmental risk in coastal soils depending on the degree of SWI. These findings have important implications for understanding soil P cycling and availability in SLR-impacted coastal areas.

Prioritizing water availability study settings to address geogenic contaminants and related societal factors.

Water availability for human and ecological uses depends on both water quantity and water quality. The U.S. Geological Survey (USGS) is developing strategies for prioritizing regional-scale and watershed basin-scale studies of water availability across the nation. Previous USGS ranking processes for basin-scale studies incorporated primarily water quantity factors but are now considering additional water quality factors. This study presents a ranking based on the potential impacts of geogenic constituents on water quality and consideration of societal factors related to water quality. High-concentration geogenic constituents, including trace elements and radionuclides, are among the most prevalent contaminants limiting water availability in the USA and globally. Geogenic constituents commonly occur in groundwater because of subsurface water-rock interactions, and their distributions are controlled by complex geochemical processes. Geogenic constituent mobility can also be affected by human activities (e.g., mining, energy production, irrigation, and pumping). Societal factors and relations to drinking water sources and water quality information are often overlooked when evaluating research priorities. Sociodemographic characteristics, data gaps resulting from historical data-collection disparities, and infrastructure condition/age are examples of factors to consider regarding environmental justice. This paper presents approaches for ranking and prioritizing potential basin-scale study areas across the contiguous USA by considering a suite of conventional physical and geochemical variables related to geogenic constituents, with and without considering variables related to societal factors. Simultaneous consideration of societal and conventional factors could provide decision makers with more diverse, interdisciplinary tools to increase equity and reduce bias in prioritizing focused research areas and future water availability studies.

Continuous cultivation of the lithoautotrophic nitrate-reducing Fe(II)-oxidizing culture KS in a chemostat bioreactor.

Laboratory-based studies on microbial Fe(II) oxidation are commonly performed for 5-10 days in small volumes with high substrate concentrations, resulting in geochemical gradients and volumetric effects caused by sampling. We used a chemostat to enable uninterrupted supply of medium and investigated autotrophic nitrate-reducing Fe(II)-oxidizing culture KS for 24 days. We analysed Fe- and N-speciation, cell-mineral associations, and the identity of minerals. Results were compared to batch systems (50 and 700 mL-static/shaken). The Fe(II) oxidation rate was highest in the chemostat with 7.57 mM Fe(II) d-1 , while the extent of oxidation was similar to the other experimental setups (average oxidation of 92% of all Fe(II)). Short-range ordered Fe(III) phases, presumably ferrihydrite, precipitated and later goethite was detected in the chemostat. The 1 mM solid phase Fe(II) remained in the chemostat, up to 15 µM of reactive nitrite was measured, and 42% of visualized cells were partially or completely mineral-encrusted, likely caused by abiotic oxidation of Fe(II) by nitrite. Despite (partial) encrustation, cells were still viable. Our results show that even with similar oxidation rates as in batch cultures, cultivating Fe(II)-oxidizing microorganisms under continuous conditions reveals the importance of reactive nitrogen intermediates on Fe(II) oxidation, mineral formation and cell-mineral interactions.

Effect of Natural Organic Matter on the Fate of Cadmium During Microbial Ferrihydrite Reduction.

Natural organic matter (NOM) is known to affect the microbial reduction and transformation of ferrihydrite, but its implication toward cadmium (Cd) associated with ferrihydrite is not well-known. Here, we investigated how Cd is redistributed when ferrihydrite undergoes microbial reduction in the presence of NOM. Incubation with Geobacter sulfurreducens showed that both the rate and the extent of reduction of Cd-loaded ferrihydrite were enhanced by increasing concentrations of NOM (i.e., C/Fe ratio). Without NOM, only 3-4% of Fe(III) was reduced, but around 61% of preadsorbed Cd was released into solution due to ferrihydrite transformation to lepidocrocite. At high C/Fe ratio (1.6), more than 35% of Fe(III) was reduced, as NOM can facilitate bioreduction by working as an electron shuttle and decreased aggregate size, but only a negligible amount of Cd was released into solution, thus decreasing Cd toxicity and prolonging microbial Fe(III) reduction. No ferrihydrite transformation was observed at high C/Fe ratios using Mössbauer spectroscopy and X-ray diffraction, and X-ray absorption spectroscopy indicated the proportion of Cd-OM bond increased after microbial reduction. This study shows that the presence of NOM leads to less mobilization of Cd under reducing condition possibly by inhibiting ferrihydrite transformation and recapturing Cd through Cd-OM bond.

Effect of Microbial Biomass and Humic Acids on Abiotic and Biotic Magnetite Formation.

Magnetite (Fe3O4) is an environmentally ubiquitous mixed-valent iron (Fe) mineral, which can form via biotic or abiotic transformation of Fe(III) (oxyhydr)oxides such as ferrihydrite (Fh). It is currently unclear whether environmentally relevant biogenic Fh from Fe(II)-oxidizing bacteria, containing cell-derived organic matter, can transform to magnetite. We compared abiotic and biotic transformation: (1) abiogenic Fh (aFh); (2) abiogenic Fh coprecipitated with humic acids (aFh-HA); (3) biogenic Fh produced by phototrophic Fe(II)-oxidizer Rhodobacter ferrooxidans SW2 (bFh); and (4) biogenic Fh treated with bleach to remove biogenic organic matter (bFh-bleach). Abiotic or biotic transformation of Fh was promoted by Feaq2+ or Fe(III)-reducing bacteria. Feaq2+-catalyzed abiotic reaction with aFh and bFh-bleach led to complete transformation to magnetite. In contrast, aFh-HA only partially (68%) transformed to magnetite, and bFh (17%) transformed to goethite. We hypothesize that microbial biomass stabilized bFh against reaction with Feaq2+. All four Fh substrates were transformed into magnetite during biotic reduction, suggesting that Fh remains bioavailable even when associated with microbial biomass. Additionally, there were poorly ordered magnetic components detected in the biogenic end products for aFh and aFh-HA. Nevertheless, abiotic transformation was much faster than biotic transformation, implying that initial Feaq2+ concentration, passivation of Fh, and/or sequestration of Fe(II) by bacterial cells and associated biomass play major roles in the rate of magnetite formation from Fh. These results improve our understanding of factors influencing secondary mineralization of Fh in the environment.

Role of biogenic Fe(III) minerals as a sink and carrier of heavy metals in the Rio Tinto, Spain.

Oxidation of sulfide ores in the Iberian Pyrite Belt region leads to the presence of extremely high concentration of dissolved heavy metals (HMs) in the acidic water of the Rio Tinto. Fe(II) is microbially oxidized resulting in the formation of suspended particulate matter (SPM) consisting of microbial cells and Fe(III) minerals with co-precipitated HMs. Although substantial amount of HM-bearing SPM is likely deposited to river sediment, a portion can still be transported through estuary to the coastal ocean. Therefore, the mechanisms of SPM formation and transport along the Rio Tinto are important for coastal-estuarine zone. In order to reveal these mechanisms, we performed diurnal sampling of Rio Tinto water, mineralogical and elemental analysis of sediment from the middle course and the estuary of the river. We identified two divergent but interrelated pathways of HM transfer. The first longitudinal pathway is the transport of SPM-associated metals such as As (6.58 µg/L), Pb (3.51 µg/L) and Cr (1.30 µg/L) to the coastal ocean. The second sedimentation pathway contributes to the continuous burial of HMs in the sediment throughout the river. In the middle course, sediment undergoes mineralogical transformations during early diagenesis and traps HMs (e.g. 1.6 mg/g of As, 1.23 mg/g of Pb and 0.1 mg/g of Cr). In the estuary, HMs are accumulated in a distinct anoxic layer of sediment (e.g. 1.5 mg/g of As, 2.09 mg/g of Pb and 0.04 mg/g of Cr). Our results indicate that microbially precipitated Fe(III) minerals (identified as ferrihydrite and schwertmannite) play a key role in maintaining these divergent HM pathways and as a consequence are crucial for HM mobility in the Rio Tinto.

Mineral Defects Enhance Bioavailability of Goethite toward Microbial Fe(III) Reduction.

Surface defects have been shown to facilitate electron transfer between Fe(II) and goethite (α-FeOOH) in abiotic systems. It is unclear, however, whether defects also facilitate microbial goethite reduction in anoxic environments where electron transfer between cells and Fe(III) minerals is the limiting factor. Here, we used stable Fe isotopes to differentiate microbial reduction of goethite synthesized by hydrolysis from reduction of goethite that was further hydrothermally treated to remove surface defects. The goethites were reduced by Geobacter sulfurreducens in the presence of an external electron shuttle, and we used ICP-MS to distinguish Fe(II) produced from the reduction of the two types of goethite. When reduced separately, goethite with more defects has an initial rate of Fe(III) reduction about 2-fold higher than goethite containing fewer defects. However, when reduced together, the initial rate of reduction is 6-fold higher for goethite with more defects. Our results suggest that there is a suppression of the reduction of goethite with fewer defects in favor of the reduction of minerals with more defects. In the environment, minerals are likely to contain defects and our data demonstrates that even small changes at the surface of iron minerals may change their bioavailability and determine which minerals will be reduced.

Use of Routine Soil Tests to Estimate Pb Bioaccessibility.

Soil lead (Pb) hazard level is contingent on bioavailability, but existing assays that estimate Pb bioavailability for human health risks are too expensive or otherwise inaccessible to many people that are impacted by Pb-contaminated soil. This study investigated the use of routine soil nutrient tests to estimate soil-Pb bioaccessibility as a surrogate measure of Pb bioavailability. A silt loam soil was spiked to a target concentration of 2000 mg Pb kg-1 with Pb(NO3)2 and amended with H3PO4 (varying P-to-Pb molar ratios) and KCl (Cl-to-P molar ratio of 2:5) to generate soils with similar total Pb concentrations but a range of Pb bioavailability (and bioaccessibility). Soils were extracted using Mehlich 3, Mehlich 1, Bray P1, Olsen, and  micronutrient (DTPA) methods, and the results were compared to U.S. Environmental Protection Agency method 1340 data as well as to extended X-ray absorption fine structure (EXAFS) spectroscopy. The Mehlich 3 and method 1340 treatment effect ratios were well-correlated ( r2 = 0.88, p ≤ 0.05), whereas Bray P1, DTPA, and Olsen results were more reflective of EXAFS data. Preliminary animal-feeding trials suggest that the Mehlich 3 is as effective as method 1340 at predicting the impact of P treatment on Pb relative bioavailability; however, both methods over-estimated the Pb hazard to mice in P-amended soil. Other routine soil tests that have heightened sensitivity to P amendment (e.g., Bray P1) may be promising candidates for Pb bioaccessibility assessment.

Decreased Electron Transfer between Cr(VI) and AH2DS in the Presence of Goethite.

9,10-Anthraquinone-2,6-disulfonic acid (AQDS) is commonly used as a model species to examine the influence of quinones on different biogeochemical cycles. The reduced form of this quinone, AHDS, can donate electrons to the toxic metal species Cr(VI), leading to the precipitation of less soluble Cr(III) phases. Due to the environmental abundance of Fe(III) (oxyhydr)oxides, such as goethite (α-FeOOH), it is important to study the role of these mineral phases on the electron transfer reaction between AHDS and Cr(VI). In this study, this electron transfer reaction is examined in the presence and absence of goethite at three different ratios of AHDS/Cr(VI). Ultraviolet-visible spectroscopy is used to qualitatively assess the oxidation state of AQDS during reactions with goethite. Iron K-edge and Cr K-edge X-ray absorption spectroscopy are used to examine the role of goethite in electron transfer and identify Cr(III) phases that form. Goethite inhibits the extent of Cr(VI) reduction to Cr(III), most notably at the highest ratio of AHDS/Cr(VI) investigated. Production of semiquinone radical species may limit electron transfer and decrease the yields of Fe(II) and Cr(III), both in the presence and absence of goethite. Understanding abiotic electron transfer reactions that occur in systems with multiple redox active species is important to determine the contribution of abiotic redox reactions to Fe biogeochemical cycling in natural soils.