Abstract  The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO3-(no inhibition) < Cl-(250 mg/L) = SO42- < PO43-for HP/ZVA and Cl-(250 mg/L; no inhibition) < NO3- < SO42- < PO43-for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.

Abstract  Basil (Ocimum basilicum L.) comprises green and purple cultivars, worldwide cultivated and appreciated for high contents of rosmarinic acid and anthocyanins, respectively. Although nitrogen (N) fertilization is needed for high yields, in basil it could have detrimental effects on the accumulation of phenolic compounds. In this study, plants of the cultivars ‘Italiano Classico’ (green) and ‘Red Rubin’ (purple) were grown in hydroponics and subjected to different nutritional treatments, consisting in N starvation, and nitrate (NO3-) or ammonium (NH4+) nutrition. Plant growth and nutritional status, estimated by the contents of NO3-, NH4+, and amino acids in roots and leaves, were evaluated and put in relation with quality traits of basil leaves, such as chlorophyll content, antioxidant capacity, total phenols, the activity of phenylalanine ammonia-lyase, and the concentrations of individual (poly)phenolic acids and flavonoids. This study reveals that N starvation, as well as the availability of the two inorganic N forms, differently affect the phenolic composition in the two cultivars. Compared to plants grown in NO3- availability, in NH4+ availability, green basil showed a higher content of (poly)phenolic acids, while in purple basil, an increase in the contents of anthocyanins was detected. Overall, the study suggests that the management of NH4+ supply could contribute to enhance crop quality in hydroponics, and provides new knowledge about the relationship between N nutrition and phenolic metabolism in basil.

Abstract  The contribution of prenatal hypoxic damage to the CNS to the formation of high sensitivity of the body to lead acetate was studied. Prenatal fetal hypoxia was modeled by the administration of sodium nitrite in doses of 5, 25, and 50 mg/kg to pregnant female rats. Cognitive capacities of mature offspring were evaluated in the radial maze test and Morris water maze test. After attaining learning criterion in the radial maze, lead acetate in a dose of 80 mg/kg was added to the drinking water of all animals over 2 weeks. Testing was performed during the exposure to the agent until disruption of the conditioned behavior. It was found that severe prenatal hypoxia (induced by the administration of 50 mg/kg sodium nitrite) impaired spatial memory, increased latency of funding the platform in Morris water maze test, and serves as a factor contributing to earlier manifestations of the neurotoxic effects of lead acetate.

Abstract  In order to evaluate the potential impact of the Arctic anthropogenic emission sources it is essential to understand better the natural aerosol sources of the inner Arctic and the atmospheric processing of the aerosols during their transport in the Arctic atmosphere. A 1-year time series of chemically specific measurements of the sub-micrometre aerosol during 2015 has been taken at the Mt. Zeppelin observatory in the European Arctic. A source apportionment study combined measured molecular tracers as source markers, positive matrix factorization, analysis of the potential source distribution and auxiliary information from satellite data and ground-based observations. The annual average sub-micrometre mass was apportioned to regional background secondary sulphate (56%), sea spray (17%), biomass burning (15%), secondary nitrate (5.8%), secondary marine biogenic (4.5%), mixed combustion (1.6%), and two types of marine gel sources (together 0.7%). Secondary nitrate aerosol mainly contributed towards the end of summer and during autumn. During spring and summer, the secondary marine biogenic factor reached a contribution of up to 50% in some samples. The most likely origin of the mixed combustion source is due to oil and gas extraction activities in Eastern Siberia. The two marine polymer gel sources predominantly occurred in autumn and winter. The small contribution of the marine gel sources at Mt. Zeppelin observatory in summer as opposed to regions closer to the North Pole is attributed to differences in ocean biology, vertical distribution of phytoplankton, and the earlier start of the summer season.

Abstract  Process-based numerical models are a useful tool for studying marine ecosystems and associated biogeochemical processes in ice-covered regions where observations are scarce. To this end, CSIB v1 (Canadian Sea-ice Biogeochemistry version 1), a new sea-ice biogeochemical model, has been developed and embedded into the Nucleus for European Modelling of the Ocean (NEMO) modelling system. This model consists of a three-compartment (ice algae, nitrate, and ammonium) sea-ice ecosystem and a two-compartment (dimethylsulfoniopropionate and dimethylsulfide) sea-ice sulfur cycle which are coupled to pelagic ecosystem and sulfur-cycle models at the sea-ice-ocean interface. In addition to biological and chemical sources and sinks, the model simulates the horizontal transport of biogeochemical state variables within sea ice through a one-way coupling to a dynamic-thermodynamic sea-ice model (LIM2; the Louvain-la-Neuve Sea Ice Model version 2). The model results for 1979 (after a decadal spin-up) are presented and compared to observations and previous model studies for a brief discussion on the model performance. Furthermore, this paper provides discussion on technical aspects of implementing the sea-ice biogeochemistry and assesses the model sensitivity to (1) the temporal resolution of the snowfall forcing data, (2) the representation of light penetration through snow, (3) the horizontal transport of sea-ice biogeochemical state variables, and (4) light attenuation by ice algae. The sea-ice biogeochemical model has been developed within the generic framework of NEMO to facilitate its use within different configurations and domains, and can be adapted for use with other NEMO-based sub-models such as LIM3 (the Louvain-la-Neuve Sea Ice Model version 3) and PISCES (Pelagic Interactions Scheme for Carbon and Ecosystem Studies).

Abstract  Nitrate and lipids have been recognized as effective dietary additives to reduce enteric CH4 production. The objective of this experiment was to evaluate the effects of nitrate (NO3¯) and canola oil, alone or in combination, on enteric methane (CH4), volatile fatty acid (VFA) concentrations, digesta kinetics and outflow of DM and microbial non-ammonia nitrogen (MicNAN) from the rumen of cattle. Four rumen-cannulated steers were used in the experiment which was designed as 4 × 4 Latin Square with four 21-d periods and four treatments. Dietary treatments consisted of a control diet (CON: 400 g/kg lucerne chaff and 600 g/kg barley grain), NO3¯ (CON + 20 g NO3¯/kg), O (CON + 50 g canola oil/kg), and NO3¯+O (CON + 20 g NO3¯/kg + 50 g canola oil/kg) with all inclusions expressed as g/kg as-fed. Exogenous markers (Co-EDTA, Yb-acetate and 15NH4Cl) were continuously infused into the rumen over 4 d to estimate digesta flow and rumen N outflow while whole tract digestibility (DMD) was determined using chromic oxide. Compared with the CON diet, feeding the NO3¯+O diet reduced (P < 0.01) methane yield (MY, g CH4/kg DMI) by 25%, daily methane production (DMP, g CH4/d) by 26% (P < 0.01) and the rumen mean retention time (MRT; P < 0.05). Nitrate containing diets reduced DMD (P < 0.01). Total VFA did not differ between treatments (P > 0.05) but NO3¯-containing diets increased acetate proportion (P < 0.01) whereas feeding the O diet increased propionate proportion (P < 0.01). Oil-containing diets reduced rumen volume (P < 0.01). The rumen protozoa concentration was reduced by including NO3¯ and canola oil alone or in combination in the diet of cattle (P < 0.05). This experiment demonstrates that feeding NO3¯+O has a synergistic effect on reducing methanogenesis from beef cattle which is consistent with NO3¯ and canola oil having complementary mechanisms for suppressing enteric CH4 production. Reducing methanogenesis by feeding NO3¯+O in this experiment did not improve the flow of MicNAN from the rumen (g MicNAN/d), microbial growth efficiency (g MicNAN/digestible organic matter intake, DOMI) or the proportion of microbial N derived from rumen NH3.

Abstract  Freshwater harmful algal blooms (HABs), driven by nutrient inputs from anthropogenic sources, pose unique risks to human and ecological health worldwide. A major nutrient contributor is agricultural land use, specifically tile drainage discharge. Small lakes and ponds are at elevated risk for HAB appearance, as they are uniquely sensitive to nutrient input. HABs introduce exposure risk to microcystin (MC), hepatotoxic and potentially carcinogenic cyanotoxins. To investigate the impact of anthropogenic land use on small lakes and ponds, 24 sites in central Ohio were sampled over a 3-month period in late summer of 2015. MC concentration, microbial community structure, and water chemistry were analyzed. Land use intensity, including tile drainage systems, was the driver of clustering in principle component analysis, ultimately contributing to nutrient deposition, a driver of HABs. Relative abundance of HAB-forming genera was correlated with elevated concentrations of nitrate and soluble reactive phosphate. One location (FC) showed MC concentrations exceeding 875 μg/L and large community shifts in ciliates (Oligohymenophorea) associated with hypoxic conditions. The prokaryotic community at FC was dominated by Planktothrix sp. These results demonstrate the impact of HABs in small lakes and ponds, and that prevailing issues extend beyond cyanotoxins, such as cascading impacts on other trophic levels.

Abstract  The energy reforms implemented in Mexico promote the use of ethanol in gasoline but exclude the country's ozone nonattainment areas oxygenated with methyl-tert-butyl ether (MTBE) in view that further scientific studies are required. To address a potential implementation scenario in areas of ozone high VOC-sensitive regimes, the impact on performance and emissions characteristics between the regular MTBE fuel available and a formulated gasoline containing 10% v/v ethanol having similar Reid vapor pressure (RVP) were compared in a single cylinder spark-ignited engine and a set of tier I vehicles. Included in the assessment were the "criteria" pollutants (THC, CO, and NOx), toxic compounds, and speciated hydrocarbons in order to calculate the ozone-forming potential (OFP). The change in combustion speed of ethanol fuel vs. regular gasoline seems to be small and depends mainly on base gasoline formulation. Vehicle dynamometer testing showed no statistically significant differences in the average THC, CO, and NOx results when comparing both fuels. Statistically significant differences were seen in total speciated hydrocarbons, total carbonyls emitted, the increases in acetaldehyde emissions, and the decreases in OFP with E10. The results show roughly 20% increase in evaporative emissions when E10 is used, but the OFP of the emissions is lower than that of the Metropolitan Area of Mexico City fuel (MAMC). The increase in the oxygen content using ethanol fuel seems to have no deleterious effect on the vintage of vehicles tested. Taking into consideration that the evaporative emissions standard in Mexico is less stringent than that in other countries, the substitution of the actual regular gasoline for ethanol fuels should uphold the least volatile AA class in areas with ozone problems.

Abstract  Tri-n-butyl phosphate (TBP) is most extensively used extractant in the nuclear fuel cycle. The present work investigates the effect of substituents and their role in the basicity of organophosphorus extractant on the uptake of actinides. In this connection, we have synthesized six different analogues of TBP by altering one of its butoxy group. The synthesized TBP derivatives were well characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Pu(IV) and Am(III), as well as acid uptake as a function of nitric acid ranging from 0.01 to 6 M and the data provides the comparison of their extraction behavior with that of 30% (1.1 M) tri-n-butyl phosphate under identical conditions. It was observed that distribution coefficient values strongly depend on the nature and size of the substituents. The presence of electron donating groups enhances the uptake of the actinides and the distribution coefficient values were significantly larger as compared to that of TBP. In addition, the effect of sodium nitrate on the extraction of uranium and enthalpy of extraction were also studied and revealed that the extraction process was exothermic. (C) 2017 Elsevier B.V. All rights reserved.

Abstract  A comprehensive chemical quality assessment of groundwater resources in the Talensi District has been conducted using conventional graphical methods and multivariate statistical techniques. The study sought to determine the main controls of groundwater chemistry and its suitability for domestic and irrigation purposes in the district. Silicate and carbonate mineral weathering were identified as the main controls on groundwater chemistry in the district, with reverse ion exchange also playing a role. High nitrate and lead levels observed have been associated with agrochemicals and wastewater from farms and homes. Three main flow regimes have been identified with Q-mode cluster analysis, in which mixed cation water types have been revealed, where areas designated as recharge zones are dominated by Na+ + K+-Mg2+-HCO3- fresh water types characterised by low mineralisation and pH, which evolve into Mg2+- Na+ + K+- HCO3- fresh water type with corresponding increased mineralisation of the groundwater. Based on the water quality index (WQI) technique modified for the district and an interpolation technique using ordinary kriging developed from a well-fitted exponential semivariogram for the estimated WQIs, the groundwater quality has been spatially classified as generally 'good' to 'excellent' for domestic purposes. Generally, the quality of groundwater for domestic usage deteriorates as one moves towards the north of the district, whereas waters in the east and west present the best quality. Classifications based on the United States Salinity Laboratory (USSL), Wilcox, and Doneen diagrams suggest that groundwater from the unconfined aquifers of the district is of excellent quality for irrigation purposes.

Abstract  The objectives of this study were to evaluate the physicochemical properties of drinking water sources at Ihiala, Nigeria, and to assess the water quality using the heavy metal pollution index, heavy metal evaluation index and contamination index models. Physicochemical parameters like pH, total hardness, total dissolved solids, nitrate, cyanide, residual chlorine and six metals (Al, Cd, Cr, Cu, Pb and Ni) were analyzed in the water samples, and heavy metal pollution indices computed. The spring and borehole waters had better organoleptic properties compared to stream, river and sachet waters. Total hardness, pH and nitrate were the major nonmetallic contributors to the poor water quality. The mean pollution indices were: heavy metal pollution index (HPI) 143.02 ± 71.16, heavy metal evaluation index (HEI) 7.53 ± 4.12 and contamination index (C d ) 1.53 ± 4.12. Sixty percent of the samples exceeded the critical HPI value of 100. There was significant (P < 0.01) positive correlation between HPI and C d , HPI and HEI (r = 0.886) and HEI and C d (r = 1.000). Lead contributed most to heavy metal pollution of water in the region. The quality of most water sources in Ihiala is not good for drinking.

Abstract  The major targets of constructed wetlands (CWs) during wastewater treatment include achieving high-quality effluent and maintaining stable effluent quality. Plant species diversity can increase nitrogen (N) removal efficiency and improve effluent quality by decreasing the effluent N concentrations, including nitrate (NO3--N), ammonium (NH4+-N) and total inorganic nitrogen (TIN) concentrations in CWs. However, the effect of plant diversity on the stability of effluent quality in response to perturbation in the form of an increased NH4+/NO3- ratio in influent has not been studied. This study conducted a microcosm experiment and assembled four plant species richness levels (1, 2, 3 and 4) and 15 species compositions by using 90 simulated CW microcosms to investigate the effect of plant diversity on the effluent N concentrations and their stability with an increase in the influent NH4+/NO3- ratio from 0:100 to 33:67 in the later stage of the experiment. The results showed that (1) plant species richness maintained a positive effect on effluent quality under an increased influent NH4+/NO3- ratio; (2) high species richness enhanced the stability of effluent water quality; (3) the presence of Phragmites australis in the community decreased the effluent TIN concentration and improved its stability under perturbation; and (4) the presence of Typha latifolia had a positive effect on N removal efficiency under perturbation. The establishment of communities with high plant species richness and proper species (such as P. australis) could simultaneously improve the effluent quality and stability in CWs for treating wastewater with increased NH4+/NO3- ratio.

Abstract  Feeding experiments with stable isotopes are helpful tools for investigation of metabolic fluxes and biochemical pathways. For assessing nitrogen metabolism, the heavier nitrogen isotope, [15N], has been frequently used. In plants, it is usually applied in form of [15N]-nitrate, which is assimilated mainly in leaves. Thus, methods for quantification of the [15N]-nitrate/[14N]-nitrate ratio in leaves are useful for the planning and evaluation of feeding and pulse-chase experiments. Here we describe a simple and sensitive method for determining the [15N]-nitrate to [14N]-nitrate ratio in leaves. Leaf discs (8 mm diameter, approximately 10 mg fresh weight) were sufficient for analysis, allowing a single leaf to be sampled multiple times. Nitrate was extracted with hot water and derivatized with mesitylene in the presence of sulfuric acid to nitromesitylene. The derivatization product was analyzed by gas chromatography-mass spectrometry with electron ionization. Separation of the derivatized samples required only 6 min. The method shows excellent repeatability with intraday and interday standard deviations of less than 0.9 mol%. Using the method, we show that [15N]-nitrate declines in leaves of hydroponically grown Crassocephalum crepidioides, an African orphan crop, with a biological half-life of 4.5 days after transfer to medium containing [14N]-nitrate as the sole nitrogen source.

Abstract  It was revealed that Anammox process promotes the anaerobic degradation of benzene under denitrification. This study investigates the effect of dissimilatory nitrate reduction to ammonium (DNRA) and exogenous ammonium on anaerobic ammonium oxidation bacteria (AnAOB) during the anaerobic degradation of benzene under denitrification. The results indicate that anammox occurs synergistically with organisms using the DNRA pathway, such as Draconibacterium and Ignavibacterium. Phylogenetic analysis showed 64% (16/25) and 36% (5/25) hzsB gene sequences, a specific biomarker of AnAOB, belonged to Candidatus 'Brocadia fuldiga' and Candidatus 'Kuenenia', respectively. Exogenous ammonium addition enhanced the anammox process and accelerated benzene degradation at a 1.89-fold higher average rate compared to that in the absence of exogenous ammonium and AnAOB belonged to Ca. 'Kuenenia' (84%) and Ca. 'Brocadia fuldiga' (16%). These results indicate that Ca. 'Brocadia fuldiga' could also play a role in DNRA. However, the diversity of abcA and bamA, the key anaerobic benzene metabolism biomarkers, remained unchanged. These findings suggest that anammox occurrence may be coupled with DNRA or exogenous ammonium and that anammox promotes anaerobic benzene degradation under denitrifying conditions. The results of this study contribute to understanding the co-occurrence of DNRA and Anammox and help explore their involvement in degradation of benzene, which will be crucial for directing remediation strategies of benzene-contaminated anoxic environment.

Abstract  Plants have ability to adapt themselves through altering their growth process. In the present study, we examined exogenous application of nitric oxide (NO) on nitrogen metabolism and auxin (PIN) gene expression, and its possible role in alleviation of arsenic (As) toxicity in Brassica juncea seedlings. Seven days old hydroponically grown B. juncea seedlings were exposed to AsIII (150 μM), Sodium nitroprusside (NO donor, 100 μM), AsIII + SNP and control (without metal)for 48 h. Experimental results revealed that AsIII stress: enhanced the level of nitrite, NiR activity, NO3- and NH4+content as well as NADH-GOGAT activity; but GDH level decreased; enhanced content of amino acids; upregulated gene expression level of N metabolism and downregulated polar auxin transporter genes (PIN); inhibited plant growth and morphological parameters; increased MDA, H2O2, cysteine, proline content, enzymatic antioxidants (SOD, CAT, APX; GSH, TT, NPT); and decreased nutrient content. AsIII + SNP combination reduced the accumulation of As; improved growth; chlorophyll, protein and mineral nutrient content by scavenging ROS generation; maintained amino acids content; downregulated expression of N metabolism genes and upregulated expression of auxin transporter (PIN) genes . Additional biochemical data depicts reduction in the level of nitrogen related enzymatic activities, and other stress related parameters. Overall, this study provides an integrated view that exogenous SNP (NO donor) supplementation alleviated the inhibitory role of AsIII in B. juncea seedlings by altering nutrients, amino acids and auxin redistribution via expression of nitrogen and PIN gene profiling.

Abstract  Mn(III) oxidation technology has attracted increasing interest in recent years because of its fast decontamination kinetics and second-pollution-free characteristic. Whether it can be used as a pre-oxidation step to enhance conventional coagulation process remains to be evaluated. Herein, an Fe-coagulation/sedimentation process combined with Mn(III) pre-oxidation (Mn(III)+C/S), hypochlorite pre-oxidation (Cl-2+C/S), and permanganate pre-oxidation (PM+C/S) was applied to treat simulated micro-polluted raw water. The removal performance of routine water quality indices (turbidity, dissolved organic carbon, total nitrogen, nitrate-nitrogen, ammonia-nitrogen, Pb(II), and Cr(VI)) and the emerging pollutants (acesulfame, carbamazepine, bisphenol S, and nano-ZnO) created by these three processes were researched. The mechanism of how Mn(III) pre-oxidation influences C/S was explored by identifying the transformation products of Mn(III), measuring the timely variation of flocs' zeta potential and size, and scanning flocs' micromorphology. Compared to Cl-2+C/S and PM+C/S, Mn(III)+C/S exhibited its superiority in removing dissolved organic carbon (72.9%), total nitrogen (31.74%), and emerging pollutants (21.78%-93.49%). The enhanced removal of these contaminants by Mn(III)+C/S found its explanation in the strong oxidation power of Mn(III) and the multiple roles of in-situ formed MnO2 (e.g., flocculation core, adsorption co-precipitant, and densification agent). The acute toxicity tests confirmed that water treated by Mn(III)+C/S did not show a significant change in the associated toxicity. The findings of the present study indicate that Mn(III) oxidation technology shows great potential as an alternative to pre-oxidation technology of waterworks.

Abstract  The problem of legacy alkaline high-level waste (HLW) both in the US and Russia, as a result of weapons production, has prompted studies of ligands for extraction of actinides, that could be possibly used in the future together with Cs extractants for combined HLW extraction processes. The tripodal trisulphonamide ligand 1,3,5-tris-(4-(iso-propyl)-phenylsulfamoylmethyl)benzene (4-iPr-tsa), which has pre-organised functional groups for An(III) binding was synthesised and studied for potential Sm(III) and Am(III) binding and extraction by theoretical (DFT) and experimental (extraction) methods (for Sm(III) only). Both theory and experiments suggest that even though this family of ligands shows promise for Ln(III) and An(III) binding with minima for complex formation, complexation is competing with hydrolysis, and extraction is only feasible in alkaline solutions, in the presence of high concentrations of nitrate ions. Nevertheless, up to 51.8% of Sm(III) was removed under optimal conditions (NaOH = 2 x 10(-4) M, NaNO3 = 0.1 M, [Sm](init) = 5 x 10(-5) M). Quantum chemical calculations demonstrate that the extraction of Sm(III) and Am(III) from the aqueous phase in the form of [M center dot(H2O)(4)center dot(OH)(2)center dot(NO3)] to the organic phase in the form of [M center dot 4-iPr-tsa center dot(H2O)(3)] is thermodynamically favourable. Theory also shows that Sm(III) is a reasonably good surrogate for Am(III), as the optimised structures of the Sm and Am complexes show remarkable similarities. Even though the ligand was designed with the goal of introducing favourable cation-arene interactions, along with the expected N-binding mode of the ligand in its deprotonated form, it was found that these cation-arene interactions are rather weak in this case, and coordination with O atoms of the sulphonamide, and external water molecules, is favoured instead.

Abstract  The biochemical mechanisms responsible for soil organic C (SOC) accumulation under N enrichment are not well understood. By examining two N types (NH4Cl and NaNO3) and three rates (0, 40, and 120 kg N ha(-1) yr(-1)), we investigated the concentration and distribution of SOC by using soil aggregate separation and physical fractionation of soil organic matter (SOM). The molecular composition of SOM within bulk soil and each physical fraction was determined by pyrolysis-gas chromatography-mass spectrometry. Nitrogen fertilization led to soil NO3(-)-N accumulation and intensified soil acidification. Four years of N fertilization did not change total SOC concentrations in the 0- to 20-cm depth but a high rate of NaNO3 addition increased the concentrations of fine particulate organic C and microaggregate-associated organic C by 133 and 83.4%, respectively. The change in SOC concentration was positively correlated with the change in fine particulate organic C and mineral-associated organic C concentrations. Four years of N fertilization significantly changed the molecular composition of SOM, with an increase in the relative abundance of furfural and acetic acid and a decrease in pyrrole in the mineral-associated organic matter (MAOM) fraction. Fertilization increased the furfural/pyrrole and aliphatic/aromatic ratios in the SOM and MAOM fractions, suggesting decreased stability of the passive SOM fraction. The SOC concentration was negatively correlated with the benzene/toluene ratio in both bulk soil and the MAOM fraction. Overall, exogenous N input to this subtropical plantation forest decreased the mineralization and humification of SOM, which could be detrimental to soil C accumulation.

Abstract  Recent studies have recognised highly oxygenated organic molecules (HOMs) in the atmosphere as important in the formation of secondary organic aerosol (SOA). A large number of studies have focused on HOM formation from oxidation of biogenically emitted monoterpenes. However, HOM formation from anthropogenic vapours has so far received much less attention. Previous studies have identified the importance of aromatic volatile organic compounds (VOCs) for SOA formation. In this study, we investigated several aromatic compounds, benzene (C6H6), toluene (C7H8), and naphthalene (C10H8), for their potential to form HOMs upon reaction with hydroxyl radicals (OH). We performed flow tube experiments with all three VOCs and focused in detail on benzene HOM formation in the Julich Plant Atmosphere Chamber (JPAC). In JPAC, we also investigated the response of HOMs to NOx and seed aerosol. Using a nitrate-based chemical ionisation mass spectrometer (CI-APi-TOF), we observed the formation of HOMs in the flow reactor oxidation of benzene from the first OH attack. However, in the oxidation of toluene and naphthalene, which were injected at lower concentrations, multi-generation OH oxidation seemed to impact the HOM composition. We tested this in more detail for the benzene system in the JPAC, which allowed for studying longer residence times. The results showed that the apparent molar benzene HOM yield under our experimental conditions varied from 4.1% to 14.0%, with a strong dependence on the OH concentration, indicating that the majority of observed HOMs formed through multiple OH-oxidation steps. The composition of the identified HOMs in the mass spectrum also supported this hypothesis. By injecting only phenol into the chamber, we found that phenol oxidation cannot be solely responsible for the observed HOMs in benzene experiments. When NOx was added to the chamber, HOM composition changed and many oxygenated nitrogen-containing products were observed in CI-APi-TOF. Upon seed aerosol injection, the HOM loss rate was higher than predicted by irreversible condensation, suggesting that some undetected oxygenated intermediates also condensed onto seed aerosol, which is in line with the hypothesis that some of the HOMs were formed in multi-generation OH oxidation. Based on our results, we conclude that HOM yield and composition in aromatic systems strongly depend on OH and VOC concentration and more studies are needed to fully understand this effect on the formation of HOMs and, consequently, SOA. We also suggest that the dependence of HOM yield on chamber conditions may explain part of the variability in SOA yields reported in the literature and strongly advise monitoring HOMs in future SOA studies.

Abstract  Purpose The "Hoya del Rincon de Parangueo (HRP)" is a maar that contained a perennial alkaline lake that drained in the 1980s so that a sediment with high pH and extreme salinity remained. The aim of this work was to determine how the bacterial and archaeal community was controlled by these extreme conditions.Materials and methods Sediment samples were collected from the 0-20-cm layer along a crater-wide transect. Physicochemical characteristics and the archaeal and bacterial community were determined by analysis of the 16S rRNA through Illumina sequencing.Results and discussion The sediment samples had a pH 10 and an electrolytic conductivity (EC) that ranged from 29.8 to 74.4 dSm(-1). Three archaeal and 37 bacterial phyla were detected with Euryarchaeota (relative abundance 62.7 +/- 17.6%) dominating the Archaea, and Proteobacteria (28.2 +/- 10.7%) and Actinobacteria (21.1 +/- 6.4%) the Bacteria. The most abundant archaeal genus was Candidatus Nitrososphaera while Euzebya, Halomonas, KSA1 and Planctomycetes dominated the bacterial gene. Thaumarchaeota were enriched in sediment samples with a higher Pb content and Euryarchaeota in sediment with a higher Mg content, while Crenarchaeota and Candidatus Nitrososphaera were enriched in sediment with a higher sand, total N and organic C content. Proteobacteria were enriched in sediment with a higher organic C and total N, Si and sand content, while Bacteroidetes and Planctomycetes in sediment with a higher water holding capacity and clay and Mg content. Members of KSA1 and Euzebya were enriched in sediment with a lower EC, organic C and total N content. Although a large number of bacterial and archaeal groups were correlated significantly with a range of sediment characteristics, the sediment characteristics explained the variation of only two bacterial groups > 50% (TM6 and Desulfonatronospira) using the machine learning tool random-Forest and none of the archaeal groups. Archaeal and bacterial functional guilds were dominated by ammonium oxidation and nitrite reduction.Conclusions Although the different sediment samples were dominated often by similar bacterial and archaeal groups, the measured sediment characteristics explained little of the variation found between the sampling points. The high bacterial and archaeal diversity indicated that the site might be a source of unclassified species and phylotypes with specific metabolic capacities involved in the N and S cycles.

Abstract  Nitrogen (N) emissions associated with urbanization exacerbate the atmospheric N influx to remote ecosystems - like mountains -, leading to well-documented detrimental effects on ecosystems (e.g., soil acidification, pollution of freshwaters). Here, the importance and fate of N deposition in a watershed was evaluated along a montane to urban gradient, using a multi-isotopic tracers approach (Δ17O, δ15N, δ18O of nitrate, δ2H and δ18O of water). In this setting, the montane streams had higher proportions of atmospheric nitrate compared to urban streams, and exported more atmospheric nitrate on a yearly basis (0.35 vs 0.10 kg-Nha-1yr-1). In urban areas, nitrate exports were driven by groundwater, whereas in the catchment head nitrate exports were dominated by surface runoff. The main sources of nitrate to the montane streams were microbial nitrification and atmospheric deposition, whereas microbial nitrification and sewage leakage contributed most to urban streams. Based on the measurement of δ15N and δ18O-NO3-, biological processes such as denitrification or N assimilation were not predominant in any streams in this study. The observed low δ15N and δ18O range of terrestrial nitrate (i.e., nitrate not coming from atmospheric deposition) in surface water compared to literature suggests that atmospheric deposition may be underestimated as a direct source of N.

Abstract  Nitrate concentration in most aquifers in arid and semi-arid areas has increased in the past several decades as a result of human activities. Under the predominantly oxic conditions of these aquifers, denitrification is inhibited, allowing nitrate, a soluble and stable form of nitrogen (N), to accumulate. Because of its close association with municipal and agricultural wastes, nitrate is commonly used as an indicator of anthropogenic contamination. Aquifers affected by agricultural waste may contain salts from irrigation returns and herbicides in addition to nitrates. Preventing leakage from soil to deeper parts of the aquifer is thus a priority in the sustainable management of aquifers in arid and semiarid areas. Studies report a wide range of nitrate concentrations distributed non-uniformly within the aquifer, with roughly 40% and 20% of sampled wells exceeding 50mg/L nitrate in shallow and deep parts of the aquifer respectively. In aquifers at risk of becoming contaminated, nitrate isotopes (δ15N, δ18O, Δ17O) can be used to identify the source of nitrogen as mineral or organic fertilizer, sewage, or atmospheric deposition. A variety of mathematical models (crop, hydrological, geochemical, or a combination of them) have been successful in identifying best practices that minimize N leakage without negatively affecting crop yield. In addition, field research in crop management, e.g., conservation agriculture, has yielded promising results in determining the adequate dosage and time of application of fertilizers to reduce N losses. Examples of key dryland aquifers impacted by nitrate are discussed, and some of the most pressing challenges to achieve sustainability are presented.

Abstract  The human diet is characterized by the intake of major minerals (Na, K, Ca, Mg, P, N) and trace elements (Zn, Mn, Se, Cu, Fe, Co, I, Cr, F, Pb, Cd) for their key role in many metabolic functions. Nowadays, the research of sources able to improve their intake is in continuous evolution, especially in the undeveloped countries. In this sense, wild edible herbs, commonly used since ancient times, can represent a good alternative to improve the daily human intake of minerals. In this study, four wild edible species, Rumex acetosa, Picris hieracioides, Cichorium intybus, and Plantago coronopus, were analyzed for their content in Na, K, Ca, Mg, Cu, Mn, Fe, and Zn and, besides, three domestications (named "soilless," pot, and open field) were evaluated in the analyzed species in the prospective of their commercialization as valuable sources of minerals in the human diet. Nitrate and oxalate contents were also evaluated, given their negative impact on human health. Results unveil that open field domestication allowed the plants to maintain the content of major minerals similar to those measured in wild plants, especially in C. intybus and P. hieracioides. The trace elements Cu, Mn, Fe, and Zn were not recorded at high content irrespectively to the wild collection or domestications. Finally, plants grown in the open field also accounted for a high oxalate and nitrate content, especially in R. acetosa. Further researches should be aimed at decreasing the oxalate and nitrate content in the domesticated species and to promote the commercialization of the domesticated species.

Abstract  Beach closings are a growing concern in coastal regions because of serious public health and economic ramifications due to the presence of pollutants in stormwater runoff. An underground permeable filter system is proposed to treat such stormwater pollution. Selection of filter media that can treat multiple contaminants in stormwater runoff has been a challenging task. This paper investigates the effectiveness of mixed or layered filter media for the removal of mixed contaminants (nutrient and heavy metal) from synthetic stormwater. Sorption experiments were used to assess the ability of the combination of various materials (calcite, zeolite, sand, and iron filings) to remove nutrients and heavy metals. Based on the results of individual removal efficiency, four sets of combinations of media mixtures were prepared: three mixed media conditions and one layered media condition. Mixed media-1, containing higher ratio of calcite, zeolite, and iron filings, was found to achieve the highest removal efficiency of nitrate (96%), Cr (similar to 99%), and Cu (similar to 99%). Mixed media-2 removed Zn significantly with a removal efficiency higher than 99% due to the sorption capacity of iron filings and both mixed media-2 and 3 showed efficient removal of Ni (similar to 94%) in effluent. Layered media was found to be most efficient in Cd removal (similar to 99%). All mixture of materials showed more than 99% removal of total phosphorus and Pb. The sorption efficiency of the different mixtures showed that a combination of traditional (sand) and alternative materials (calcite, zeolite, and iron filings) can be used as an effective medium for the treatment of nutrient and heavy metal contaminants commonly found in stormwater.