Transfer of sulfur and chalcophile metals via sulfide-volatile compound drops in the Christiana-Santorini-Kolumbo volcanic field.

Efficient transfer of S and chalcophile metals through the Earth's crust in arc systems is paramount for the formation of large magmatic-hydrothermal ore deposits. The formation of sulfide-volatile compound drops has been recognized as a potential key mechanism for such transfer but their fate during dynamic arc magmatism remains cryptic. Combining elemental mapping and in-situ mineral analyzes we reconstruct the evolution of compound drops in the active Christiana-Santorini-Kolumbo volcanic field. The observed compound drops are micrometric sulfide blebs associated with vesicles trapped within silicate phenocrysts. The compound drops accumulate and coalesce at mafic-felsic melt interfaces where larger sulfide ovoids form. These ovoids are subsequently oxidized to magnetite during sulfide-volatile interaction. Comparison of metal concentrations between the sulfide phases and magnetite allows for determination of element mobility during oxidation. The formation and evolution of compound drops may be an efficient mechanism for transferring S and chalcophile metals into shallow magmatic-hydrothermal arc systems.

Jasmonate signaling controls negative and positive effectors of salt stress tolerance in rice.

Plant responses to salt exposure involve large reconfigurations of hormonal pathways that orchestrate physiological changes towards tolerance. Jasmonate (JA) hormones are essential to withstand biotic and abiotic assaults, but their roles in salt tolerance remain unclear. Here we describe the dynamics of JA metabolism and signaling in root and leaf tissue of rice, a plant species that is highly exposed and sensitive to salt. Roots activate the JA pathway in an early pulse, while the second leaf displays a biphasic JA response with peaks at 1 h and 3 d post-exposure. Based on higher salt tolerance of a rice JA-deficient mutant (aoc), we examined, through kinetic transcriptome and physiological analysis, the salt-triggered processes that are under JA control. Profound genotype-differential features emerged that could underlie the observed phenotypes. Abscisic acid (ABA) content and ABA-dependent water deprivation responses were impaired in aoc shoots. Moreover, aoc accumulated more Na+ in roots, and less in leaves, with reduced ion translocation correlating with root derepression of the HAK4 Na+ transporter gene. Distinct reactive oxygen species scavengers were also stronger in aoc leaves, along with reduced senescence and chlorophyll catabolism markers. Collectively, our results identify contrasted contributions of JA signaling to different sectors of the salt stress response in rice.

Gain time to adapt: How sorghum acquires tolerance to salinity.

Salinity is a global environmental threat to agricultural production and food security around the world. To delineate salt-induced damage from adaption events we analysed a pair of sorghum genotypes which are contrasting in their response to salt stress with respect to physiological, cellular, metabolomic, and transcriptional responses. We find that the salt-tolerant genotype Della can delay the transfer of sodium from the root to the shoot, more swiftly deploy accumulation of proline and antioxidants in the leaves and transfer more sucrose to the root as compared to its susceptible counterpart Razinieh. Instead Razinieh shows metabolic indicators for a higher extent photorespiration under salt stress. Following sodium accumulation by a fluorescent dye in the different regions of the root, we find that Della can sequester sodium in the vacuoles of the distal elongation zone. The timing of the adaptive responses in Della leaves indicates a rapid systemic signal from the roots that is travelling faster than sodium itself. We arrive at a model where resistance and susceptibility are mainly a matter of temporal patterns in signalling.

The jasmonate biosynthesis Gene OsOPR7 can mitigate salinity induced mitochondrial oxidative stress.

Salinity poses a serious threat to global agriculture and human food security. A better understanding of plant adaptation to salt stress is, therefore, mandatory. In the non-photosynthetic cells of the root, salinity perturbs oxidative balance in mitochondria, leading to cell death. In parallel, plastids accumulate the jasmonate precursor cis (+)12-Oxo-Phyto-Dienoic Acid (OPDA) that is then translocated to peroxisomes and has been identified as promoting factor for salt-induced cell death as well. In the current study, we probed for a potential interaction between these three organelles that are primarily dealing with oxidative metabolism. We made use of two tools: (i) Rice OPDA Reductase 7 (OsOPR7), an enzyme localised in peroxisomes converting OPDA into the precursors of the stress hormone JA-Ile. (ii) A Trojan Peptoid, Plant PeptoQ, which can specifically target to mitochondria and scavenge excessive superoxide accumulating in response to salt stress. We show that overexpression of OsOPR7 as GFP fusion in tobacco (Nicotiana tabacum L. cv. Bright Yellow 2, BY-2) cells, as well as a pretreatment with Plant PeptoQ can mitigate salt stress with respect to numerous aspects including proliferation, expansion, ionic balance, redox homeostasis, and mortality. This mitigation correlates with a more robust oxidative balance, evident from a higher activity of superoxide dismutase (SOD), lower levels of superoxide and lipid peroxidation damage, and a conspicuous and specific upregulation of mitochondrial SOD transcripts. Although both, Plant PeptoQ and ectopic OsOPR7, were acting in parallel and mostly additive, there are two specific differences: (i) OsOPR7 is strictly localised to the peroxisomes, while Plant PeptoQ found in mitochondria. (ii) Plant PeptoQ activates transcripts of NAC, a factor involved in retrograde signalling from mitochondria to the nucleus, while these transcripts are suppressed significantly in the cells overexpressing OsOPR7. The fact that overexpression of a peroxisomal enzyme shifting the jasmonate pathway from the cell-death signal OPDA towards JA-Ile, a hormone linked with salt adaptation, is accompanied by more robust redox homeostasis in a different organelle, the mitochondrion, indicates that cross-talk between peroxisome and mitochondrion is a crucial factor for efficient adaptation to salt stress.

Starve to Sustain-An Ancient Syrian Landrace of Sorghum as Tool for Phosphorous Bio-Economy?

Phosphorus (P) is an essential macronutrient, playing a role in developmental and metabolic processes in plants. To understand the local and systemic responses of sorghum to inorganic phosphorus (Pi) starvation and the potential of straw and ash for reutilisation in agriculture, we compared two grain (Razinieh) and sweet (Della) sorghum varieties with respect to their morpho-physiological and molecular responses. We found that Pi starvation increased the elongation of primary roots, the formation of lateral roots, and the accumulation of anthocyanin. In Razinieh, lateral roots were promoted to a higher extent, correlated with a higher expression of SbPht1 phosphate transporters. Infrared spectra of straw from mature plants raised to maturity showed two prominent bands at 1371 and 2337 cm-1, which could be assigned to P-H(H2) stretching vibration in phosphine acid and phosphinothious acid, and their derivates, whose abundance correlated with phosphate uptake of the source plant and genotype (with a higher intensity in Razinieh). The ash generated from these straws stimulated the shoot elongation and root development of the rice seedlings, especially for the material derived from Razinieh raised under Pi starvation. In conclusion, sorghum growing on marginal lands has potential as a bio-economy alternative for mineral phosphorus recycling.

Carbon and methane cycling in arsenic-contaminated aquifers.

Geogenic arsenic (As) contamination of groundwater is a health threat to millions of people worldwide, particularly in alluvial regions of South and Southeast Asia. Mitigation measures are often hindered by high heterogeneities in As concentrations, the cause(s) of which are elusive. Here we used a comprehensive suite of stable isotope analyses and hydrogeochemical parameters to shed light on the mechanisms in a typical high-As Holocene aquifer near Hanoi where groundwater is advected to a low-As Pleistocene aquifer. Carbon isotope signatures (δ13C-CH4, δ13C-DOC, δ13C-DIC) provided evidence that fermentation, methanogenesis and methanotrophy are actively contributing to the As heterogeneity. Methanogenesis occurred concurrently where As levels are high (>200 µg/L) and DOC-enriched aquitard pore water infiltrates into the aquifer. Along the flowpath to the Holocene/Pleistocene aquifer transition, methane oxidation causes a strong shift in δ13C-CH4 from -87‰ to +47‰, indicating high reactivity. These findings demonstrate a previously overlooked role of methane cycling and DOC infiltration in high-As aquifers.

Fermentation, methanotrophy and methanogenesis influence sedimentary Fe and As dynamics in As-affected aquifers in Vietnam.

High arsenic (As) concentrations in groundwater are a worldwide problem threatening the health of millions of people. Microbial processes are central in the (trans)formation of the As-bearing ferric and ferrous minerals, and thus regulate dissolved As levels in many aquifers. Mineralogy, microbiology and dissolved As levels can vary sharply within aquifers, making high-resolution measurements particularly valuable in understanding the linkages between them. We conducted a high spatial resolution geomicrobiological study in combination with analysis of sediment chemistry and mineralogy in an alluvial aquifer system affected by geogenic As in the Red River delta in Vietnam. Microbial community analysis revealed a dominance of fermenters, methanogens and methanotrophs whereas sediment mineralogy along a 46 m deep core showed a diversity of Fe minerals including poorly crystalline Fe (II/III) and Fe(III) (oxyhydr)oxides such as goethite, hematite, and magnetite, but also the presence of Fe(II)-bearing carbonates and sulfides which likely formed as a result of microbially driven organic carbon (OC) degradation. A potential important role of methane (CH4) as electron donor for reductive Fe mineral (trans)formation was supported by the high abundance of Candidatus Methanoperedens, a known Fe(III)-reducing methanotroph. Overall, these results imply that OC turnover including fermentation, methanogenesis and CH4 oxidation are important mechanisms leading to Fe mineral (trans)formation, dissolution and precipitation, and thus indirectly affecting As mobility by changing the Fe-mineral inventory.

Microbial transformation of biogenic and abiogenic Fe minerals followed by in-situ incubations in an As-contaminated vs. non-contaminated aquifer.

Fe(III) minerals play a crucial role for arsenic (As) mobility in aquifers as they usually represent the main As-bearing phases. Microbial reductive dissolution of As-bearing Fe(III) minerals is responsible for the release of As and the resulting groundwater contamination in many sites worldwide. So far, in most studies mainly abiogenic iron minerals have been considered. Yet, biogenic minerals that possess different properties to their abiogenic counterparts are also present in the environment. In some environments they dominate the iron mineral inventory but so far, it is unclear what this means for the As mobility. We, therefore, performed an in-situ aquifer Fe(III) minerals exposure experiment i) to evaluate how different biogenic and abiogenic Fe(III) minerals are transformed in a strongly reducing, As-contaminated aquifer (25 m) compared to As-free moderately reducing aquifer (32 m) and ii) to assess which microbial taxa are involved in these Fe(III) minerals transformations. We found that higher numbers of bacteria and archaea were associated with the minerals incubated in the As-contaminated compared to the non-contaminated aquifer and that all Fe(III) minerals were mainly colonized by Fe(III)-reducing bacteria, with Geobacter being the most abundant taxon. Additionally, fermenting microorganisms were abundant on minerals incubated in the As-contaminated aquifer, while methanotrophs were identified on the minerals incubated in the As-free moderately reducing aquifer, implying involvement of these microorganisms in Fe(III) reduction. We observed that biogenic Fe(III) minerals generally tend to become more reduced and when incubated in the As-contaminated aquifer sorbed more As than the abiogenic ones. Most of abiogenic and biogenic Fe(III) minerals were transformed into magnetite while biogenic more crystalline mixed phases were not subjected to visible transformation. This in-situ Fe(III) minerals incubation approach shows that biogenic minerals are more prone to be colonized by (Fe(III)-reducing) microorganisms and bind more As, although ultimately produce similar minerals during Fe(III) reduction.

Phosphate immobilisation dynamics and interaction with arsenic sorption at redox transition zones in floodplain aquifers: Insights from the Red River Delta, Vietnam.

Although phosphate (PO43-) may play a decisive role in enriching toxic arsenic (As) in the groundwater of many Asian deltas, knowledge gaps exist regarding its interactions with As. This study investigates the simultaneous immobilisation of PO43- and As in aquifer sediments at a redox transition zone in the Red River Delta of Vietnam. The majority of PO43- and As was found to be structurally bound in layers of Fe(III)-(oxyhydr)oxide precipitates, indicating that their formation represents a dominant immobilisation mechanism. This immobilisation was also closely linked to sorption. In the surface sorbed sediment pools, the molar ratios of total P to As were one order of magnitude higher than found in groundwater, reflecting a preferential sorption of PO43- over As. However, this competitive sorption was largely dependent on the presence of Fe(III)-(oxyhydr)oxides. Ongoing contact of the aquifer sediments with iron-reducing groundwater resulted in the reductive dissolution of weakly crystalline Fe(III)-(oxyhydr)oxides, which was accompanied by decreased competition for sorption sites between PO43- and As. Our results emphasise that, to be successful in the medium and long term, remediation approaches and management strategies need to consider competitive sorption between PO43- and As and dynamics of the biogeochemical Fe-cycle.

A mitochondria-targeted coenzyme Q peptoid induces superoxide dismutase and alleviates salinity stress in plant cells.

Salinity is a serious challenge to global agriculture and threatens human food security. Plant cells can respond to salt stress either by activation of adaptive responses, or by programmed cell death. The mechanisms deciding the respective response are far from understood, but seem to depend on the degree, to which mitochondria can maintain oxidative homeostasis. Using plant PeptoQ, a Trojan Peptoid, as vehicle, it is possible to transport a coenzyme Q10 (CoQ10) derivative into plant mitochondria. We show that salinity stress in tobacco BY-2 cells (Nicotiana tabacum L. cv Bright Yellow-2) can be mitigated by pretreatment with plant PeptoQ with respect to numerous aspects including proliferation, expansion, redox homeostasis, and programmed cell death. We tested the salinity response for transcripts from nine salt-stress related-genes representing different adaptive responses. While most did not show any significant response, the salt response of the transcription factor NtNAC, probably involved in mitochondrial retrograde signaling, was significantly modulated by the plant PeptoQ. Most strikingly, transcripts for the mitochondrial, Mn-dependent Superoxide Dismutase were rapidly and drastically upregulated in presence of the peptoid, and this response was disappearing in presence of salt. The same pattern, albeit at lower amplitude, was seen for the sodium exporter SOS1. The findings are discussed by a model, where plant PeptoQ modulates retrograde signalling to the nucleus leading to a strong expression of mitochondrial SOD, what renders mitochondria more resilient to perturbations of oxidative balance, such that cells escape salt induced cell death and remain viable.

Effects of metal cation substitution on hexavalent chromium reduction by green rust.

Chromium contamination is a serious environmental issue in areas affected by leather tanning and metal plating, and green rust sulfate has been tested extensively as a potential material for in situ chemical reduction of hexavalent chromium in groundwater. Reported products and mechanisms for the reaction have varied, most likely because of green rust's layered structure, as reduction at outer and interlayer surfaces might produce different reaction products with variable stabilities. Based on studies of Cr(III) oxidation by biogenic Mn (IV) oxides, Cr mobility in oxic soils is controlled by the solubility of the Cr(III)-bearing phase. Therefore, careful engineering of green rust properties, i.e., crystal/particle size, morphology, structure, and electron availability, is essential for its optimization as a remediation reagent. In the present study, pure green rust sulfate and green rust sulfate with Al, Mg and Zn substitutions were synthesized and reacted with identical chromate (CrO42-) solutions. The reaction products were characterized by X-ray diffraction, pair distribution function analysis, X-ray absorption spectroscopy and transmission electron microscopy and treated with synthetic δ-MnO2 to assess how easily Cr(III) in the products could be oxidized. It was found that Mg substitution had the most beneficial effect on Cr lability in the product. Less than 2.5% of the Cr(III) present in the reacted Mg-GR was reoxidized by δ-MnO2 within 14 days, and the particle structure and Cr speciation observed during X-ray scattering and absorption analyses of this product suggested that Cr(VI) was reduced in its interlayer. Reduction in the interlayer lead to the linkage of newly-formed Cr(III) to hydroxyl groups in the adjacent octahedral layers, which resulted in increased structural coherency between these layers, distinctive rim domains, sequestration of Cr(III) in insoluble Fe oxide bonding environments resistant to reoxidation and partial transformation to Cr(III)-substituted feroxyhyte. Based on the results of this study of hexavalent chromium reduction by green rust sulfate and other studies, further improvements can also be made to this remediation technique by reacting chromate with a large excess of green rust sulfate, which provides excess Fe(II) that can catalyze transformation to more crystalline iron oxides, and synthesis of the reactant under alkaline conditions, which has been shown to favor chromium reduction in the interlayer of Fe(II)-bearing phyllosilicates.

Spatial and temporal evolution of groundwater arsenic contamination in the Red River delta, Vietnam: Interplay of mobilisation and retardation processes.

Geogenic arsenic (As) contamination of groundwater poses a major threat to global health, particularly in Asia. To mitigate this exposure, groundwater is increasingly extracted from low-As Pleistocene aquifers. This, however, disturbs groundwater flow and potentially draws high-As groundwater into low-As aquifers. Here we report a detailed characterisation of the Van Phuc aquifer in the Red River Delta region, Vietnam, where high-As groundwater from a Holocene aquifer is being drawn into a low-As Pleistocene aquifer. This study includes data from eight years (2010-2017) of groundwater observations to develop an understanding of the spatial and temporal evolution of the redox status and groundwater hydrochemistry. Arsenic concentrations were highly variable (0.5-510 µg/L) over spatial scales of <200 m. Five hydro(geo)chemical zones (indicated as A to E) were identified in the aquifer, each associated with specific As mobilisation and retardation processes. At the riverbank (zone A), As is mobilised from freshly deposited sediments where Fe(III)-reducing conditions occur. Arsenic is then transported across the Holocene aquifer (zone B), where the vertical intrusion of evaporative water, likely enriched in dissolved organic matter, promotes methanogenic conditions and further release of As (zone C). In the redox transition zone at the boundary of the two aquifers (zone D), groundwater arsenic concentrations decrease by sorption and incorporations onto Fe(II) carbonates and Fe(II)/Fe(III) (oxyhydr)oxides under reducing conditions. The sorption/incorporation of As onto Fe(III) minerals at the redox transition and in the Mn(IV)-reducing Pleistocene aquifer (zone E) has consistently kept As concentrations below 10 µg/L for the studied period of 2010-2017, and the location of the redox transition zone does not appear to have propagated significantly. Yet, the largest temporal hydrochemical changes were found in the Pleistocene aquifer caused by groundwater advection from the Holocene aquifer. This is critical and calls for detailed investigations.

Tin-113 and Selenium-75 radiotracer adsorption and desorption kinetics in contrasting estuarine salinity and turbidity conditions.

Batch experiments were performed to study adsorption and desorption of 75Se and 113Sn radiotracers at environmentally representative concentrations of ~0.3 ng L-1 and ~3 ng L-1, respectively. The radiotracers were incubated with wet bulk sediments from the Gironde Estuary and the Rhône River, combining freshwater and coastal seawater salinity (S = 0, S = 32) and three different Suspended Particulate Matter (SPM) concentrations (10 mg L-1, 100 mg L-1, 1000 mg L-1) to simulate six hydrologically contrasting situations for each particle type. Results showed no measurable adsorption for 75Se under the experimental conditions, whereas >90% of 113Sn rapidly adsorbed onto the particles during the first hours of exposure. Adsorption efficiency increased with increasing SPM concentration and seemed to be slightly greater for the Rhône River sediments, potentially related to the intrinsic mineral composition. Desorption of spiked sediments exposed to filtered, unspiked freshwater and seawater only occurred for 113Sn (<15% of the previously adsorbed 113Sn) in the Garonne River sediments. This study provides insights to the potential environmental behaviour of hypothetical radionuclide releases of Se and Sn into highly dynamic and contrasting aquatic systems. Multiple accidental scenarios for the case of the Gironde Estuary and the Rhône River are discussed. These scenarios suggest that the environmental fate of soluble radionuclides like Se will be associated to water hydrodynamics and potentially more bioavailable whereas highly particle-active radionuclides like Sn will follow natural river/estuarine sedimentary regimes. Information on reactivity of radionuclides is important for improving the precision of current approaches aiming at modelling environmental radionuclide dispersion in continent-ocean transition systems.

The behaviour of irrigation induced Se in the groundwater-soil-plant system in Punjab, India.

Selenium is of special interest in different research fields due to its narrow range between beneficial and toxic effects. On a global scale, Se deficiency is more widespread. Biofortification measures have successfully been applied to specifically increase Se concentrations in food crops. Still not much is known about the behaviour and long-term fate of externally supplied Se. Over many years, natural but external selenate is regularly introduced into the soil-plant system via irrigation at our study sites in Punjab which makes it also an ideal natural analogue to investigate the long term effect of biofortification. For our study, we combined total and species specific analysis of Se in soil and plant material. Selenium is clearly enriched in all investigated topsoils (0-15 cm) with concentrations of 1.5-13.0 mg kg-1 despite similar background Se concentrations (0.5 ± 0.1 mg kg-1) below 15 cm depth. Irrigation is indicated to be the primary source of excess Se. Processes like Se species transformation, uptake by plants and plant material decomposition further influence both the Se speciation and extent of Se enrichment in the soils. The Se concentration in different plants and plant parts is alarmingly high showing concentrations of up to 738 mg kg-1 in wheat. Irrigation induced selenate can be considered as an easily available short term pool of Se for plants and thus strongly controls their total Se concentration and speciation. The long-term pool of Se in the topsoil mainly consists of selenite and organic Se species. These species are readily retained but still sufficiently mobile to be taken up by plants. The formation of elemental Se can be considered as a non-available Se pool and is thus, the major cause of Se immobilization and long-term enrichment of Se in the soils. Our study clearly shows that biofortification with selenate, despite its effectiveness, bears the risk of easily increasing Se levels in plants to toxic levels and producing food with less favourable inorganic Se species if not done with care. Excess selenate is either lost due to biomethylation or immobilized within the soil which has to be considered as highly negative from both an economic and ecological point of few.

Coupling Langmuir with Michaelis-Menten-A practical alternative to estimate Se content in rice?

Selenium plays an important, but vastly neglected role in human nutrition with a narrow gap between dietary deficiency and toxicity. For a potential biofortification of food with Se, as well as for toxicity-risk assessment in sites contaminated by Se, modelling of local and global Se cycling is essential. As bioavailability of Se for rice plants depends on the speciation of Se and the resulting interactions with mineral surfaces as well as the interaction with Se uptake mechanisms in plants, resulting plant Se content is complex to model. Unfortunately, simple experimental models to estimate Se uptake into plants from substrates have been lacking. Therefore, a mass balance of Se transfer between lithosphere (represented by kaolinite), hydrosphere (represented by a controlled nutrient solution), and biosphere (represented by rice plants) has been established. In a controlled, closed, lab-scale system, rice plants were grown hydroponically in nutrient solution supplemented with 0-10 000 µg L-1 Se of either selenate or selenite. Furthermore, in a series of batch experiments, adsorption and desorption were studied for selenate and selenite in competition with each of the major nutrient oxy-anions, nitrate, sulfate and phosphate. In a third step, the hydroponical plants experiments were coupled with sorption experiments to study synergy effects. These data were used to develop a mass balance fitting model of Se uptake and partitioning. Adsorption was well-described by Langmuir isotherms, despite competing anions, however, a certain percentage of Se always remained bio-unavailable to the plant. Uptake of selenate or selenite by transporters into the rice plant was fitted with the non-time differentiated Michaelis-Menten equation. Subsequent sequestration of Se to the shoot was better described using a substrate-inhibited variation of the Michaelis-Menten equation. These fitted parameters were then integrated into a mass balance model of Se transfer.

Biogeochemical phosphorus cycling in groundwater ecosystems - Insights from South and Southeast Asian floodplain and delta aquifers.

The biogeochemical cycling of phosphorus (P) in South and Southeast Asian floodplain and delta aquifers has received insufficient attention in research studies, even though dissolved orthophosphate (PO43-) in this region is closely linked with the widespread contamination of groundwater with toxic arsenic (As). The overarching aim of this study was to characterize the enrichment of P in anoxic groundwater and to provide insight into the biogeochemical mechanisms underlying its mobilization, subsurface transport, and microbial cycling. Detailed groundwater analyses and in situ experiments were conducted that focused on three representative field sites located in the Red River Delta (RRD) of Vietnam and the Bengal Delta Plain (BDP) in West Bengal, India. The results showed that the total concentrations of dissolved P (TDP) ranged from 0.03 to 1.50 mg L-1 in groundwater, with PO43- being the dominant P species. The highest concentrations occurred in anoxic sandy Holocene aquifers where PO43- was released into groundwater through the microbial degradation of organic carbon and the concomitant reductive dissolution of Fe(III)-(hydr)oxides. The mobilization of PO43- may still constitute an active process within shallow Holocene sediments. Furthermore, a sudden supply of organic carbon may rapidly decrease the redox potential, which causes an increase in TDP concentrations in groundwater, as demonstrated by a field experiment. Considering the subsurface transport of PO43-, Pleistocene aquifer sediments represented effective sinks; however, the enduring contact between oxic Pleistocene sediments and anoxic groundwater also changed the sediments PO43--sorption capacity over time. A stable isotope analysis of PO43--bound oxygen indicated the influences of intracellular microbial cycling as well as a specific PO43- source with a distinct isotopically heavy signal. Consequently, porous aquifers in Asian floodplain and delta regions proved to be ideal natural laboratories to study the biogeochemical cycling of P and its behavior in groundwater environments.

Different forms of osmotic stress evoke qualitatively different responses in rice.

Drought, salinity and alkalinity are distinct forms of osmotic stress with serious impacts on rice productivity. We investigated, for a salt-sensitive rice cultivar, the response to osmotically equivalent doses of these stresses. Drought, experimentally mimicked by mannitol (single factor: osmotic stress), salinity (two factors: osmotic stress and ion toxicity), and alkalinity (three factors: osmotic stress, ion toxicity, and depletion of nutrients and protons) produced different profiles of adaptive and damage responses, both locally (in the root) as well as systemically (in the shoot). The combination of several stress factors was not necessarily additive, and we even observed cases of mitigation, when two (salinity), or three stressors (alkalinity) were compared to the single stressor (drought). The response to combinations of individual stress factors is therefore not a mere addition of the partial stress responses, but rather represents a new quality of response. We interpret this finding in a model, where the output to signaling molecules is not determined by their abundance per se, but qualitatively depends on their adequate integration into an adaptive signaling network. This output generates a systemic signal that will determine the quality of the shoot response to local concentrations of ions.

Arsenic Mobilization from Historically Contaminated Mining Soils in a Continuously Operated Bioreactor: Implications for Risk Assessment.

Concentrations of soil arsenic (As) in the vicinity of the former Zloty Stok gold mine (Lower Silesia, southwest Poland) exceed 1000 µg g(-1) in the area, posing an inherent threat to neighboring bodies of water. This study investigated continuous As mobilization under reducing conditions for more than 3 months. In particular, the capacity of autochthonic microflora that live on natural organic matter as the sole carbon/electron source for mobilizing As was assessed. A biphasic mobilization of As was observed. In the first two months, As mobilization was mainly conferred by Mn dissolution despite the prevalence of Fe (0.1 wt % vs 5.4 for Mn and Fe, respectively) as indicated by multiple regression analysis. Thereafter, the sudden increase in aqueous As[III] (up to 2400 µg L(-1)) was attributed to an almost quintupling of the autochthonic dissimilatory As-reducing community (quantitative polymerase chain reaction). The aqueous speciation influenced by microbial activity led to a reduction of solid phase As species (X-ray absorption fine structure spectroscopy) and a change in the elemental composition of As hotspots (micro X-ray fluorescence mapping). The depletion of most natural dissolved organic matter and the fact that an extensive mobilization of As[III] occurred after two months raises concerns about the long-term stability of historically As-contaminated sites.

Determination of microplastic polyethylene (PE) and polypropylene (PP) in environmental samples using thermal analysis (TGA-DSC).

Microplastics are increasingly detected in the environment and the consequences on water resources and ecosystems are not clear to date. The present study provides a cost-effective and straightforward method to determine the mass concentrations of polymer types using thermal analysis. Characteristic endothermic phase transition temperatures were determined for seven plastic polymer types using TGA-DSC. Based on that, extracts from wastewater samples were analyzed. Results showed that among the studied polymers, only PE and PP could be clearly identified, while the phase transition signals of the other polymers largely overlap each other. Subsequently, calibration curves were run for PE and PP for qualitative measurements. 240 and 1540mg/m(3) of solid material (12µm to 1mm) was extracted from two wastewater effluent samples of a municipal WWTP of which 34% (81mg/m(3)) and 17% (257mg/m(3)) could be assigned to PE, while PP was not detected in any of the samples. The presented application of TGA-DSC provides a complementary or alternative method to FT-IR analyses for the determination of PE and PP in environmental samples.

Tracking Se Assimilation and Speciation through the Rice Plant - Nutrient Competition, Toxicity and Distribution.

Up to 1 billion people are affected by low intakes of the essential nutrient selenium (Se) due to low concentrations in crops. Biofortification of this micronutrient in plants is an attractive way of increasing dietary Se levels. We investigated a promising method of Se biofortification of rice seedlings, as rice is the primary staple for 3 billion people, but naturally contains low Se concentrations. We studied hydroponic Se uptake for 0-2500 ppb Se, potential phyto-toxicological effects of Se and the speciation of Se along the shoots and roots as a function of added Se species, concentrations and other nutrients supplied. We found that rice germinating directly in a Se environment increased plant-Se by factor 2-16, but that nutrient supplementation is required to prevent phyto-toxicity. XANES data showed that selenite uptake mainly resulted in the accumulation of organic Se in roots, but that selenate uptake resulted in accumulation of selenate in the higher part of the shoot, which is an essential requirement for Se to be transported to the grain. The amount of organic Se in the plant was positively correlated with applied Se concentration. Our results indicate that biofortification of seedlings with selenate is a successful method to increase Se levels in rice.