Phenol and sulfide oxidation in a denitrifying biofilm reactor and its microbial community analysis

A microbial consortium attached onto a polyethylene support was used to evaluate the simultaneous oxidation of sulfide and phenol by denitrification. The phenol, sulfide and nitrate loading rates applied to an inverse fluidized bed reactor were up to 168 mg phenol–C/(l d), 37 mg S^2?/(l d) and 168 mg NO₃^?–N/(l d), respectively. Under steady state operation the consumption efficiencies of phenol, sulfide and nitrate were 100%. The N₂ yield (g N₂/g NO₃^?–N) was 0.89. The phenol was mineralized resulting in a yield of 0.82 g bicarbonate–C/g phenol–C and sulfide was completely oxidized to sulfate with a yield of 0.99 g SO₄^2?–S/g S^2?. 16S rRNA gene-based microbial community analysis of the denitrifying biofilm showed the presence of Thauera aromatica, Thiobacillus denitrificans, Thiobacillus sajanensis and Thiobacillus sp. This is the first work reporting the simultaneous oxidation of sulfide and phenol in a denitrifying biofilm reactor.     

Control and optimization of nitrifying communities for nitritation from domestic wastewater at room temperatures

To achieve nitritation from complete-nitrification seed sludge at room temperature of 19 ± 1 °C, a lab-scale sequencing batch reactor (SBR) treating domestic wastewater with low C/N ratios was operated to investigate the control and optimization of nitrifying communities. Ammonia oxidizing bacteria (AOB) dominance was enhanced through the combination of low DO concentrations (<1.0 mg/L) and preset short-cycle control of aeration time. Nitritation was successfully established with NO₂^?-N/NO_x^?-N over 95%. To avoid the adverse impact of low DO concentrations on AOB activities, DO concentrations were increased to 1–2 mg/L. At the normal DO levels and temperatures, on-line control strategy of aerobic durations maintained the stability of nitritation with nitrite accumulation rate over 95% and ammonia removal above 97%. Fluorescence in-situ hybridization (FISH) analysis presented that the maximal percentage of AOB in biomass reached 10.9% and nitrite oxidizing bacteria (NOB) were washed out.     

Nitrate removal processes in a constructed wetland treating drainage from dairy pasture

¹⁵N-labelled NO₃^? was used in a surface-flow constructed wetland in spring to examine the relative importance of competing NO₃^? removal processes. In situ mesocosms (0.25 m²) were dosed with 2 l of ¹⁵NO₃^? (NaNO₃, 300 mg N l^?1, 99 atom% ¹⁵N) and bromide (Br^?) solution (LiBr, 4.3 g l^?1, as a conservative tracer). Concentrations of NO₃^?, Br^?, dissolved oxygen and ¹⁵N₂ were monitored periodically and replicate mesocosms were destructively sampled prior to and 6 days after ¹⁵N addition. Denitrification, immobilisation, plant uptake and dissimilatory NO₃^? reduction to NH₄⁺ (DNRA) accounted for 77, 11, 9 and 2% of ¹⁵NO₃^? transformed during the experiment. Only 6% of denitrification gases were directly measured as atmospheric or dissolved ¹⁵N₂; the remainder (71%) was determined via ¹⁵N mass balance. This indicated that a large proportion of the denitrification gases were entrapped within the soil matrix and/or plant aerenchyma. The floating plant Lemna minor exhibited a significantly higher NO₃^? uptake rate (221 mg kg^?1 d^?1) than Typha orientalis (10 mg kg^?1 d^?1), but periodic harvest of plants would remove <3% of annual NO₃^? inputs. Our results suggest that this 6-year-old constructed wetland functions effectively as a sink for NO₃^? during the growing season with less than one-quarter of the NO₃^? processed sequestered into wetland plant, algal and microbial N pools and the balance permanently removed by denitrification.     

Aerobic degradation of 2-picolinic acid by a nitrobenzene-assimilating strain: Streptomyces sp. Z2

Streptomyces sp. Z2 was isolated from nitrobenzene contaminated activated sludge, which utilized nitrobenzene as a sole source of carbon, nitrogen, and energy under aerobic condition. It was found that besides nitrobenzene strain Z2 can degrade 2-picolinic acid. Strain Z2 completely degraded 2-picolinic acid with initial concentration of 500 mg/L, 1000 mg/L, 1500 mg/L, 2000 mg/L, 2500 mg/L, and 3000 mg/L within 36 h, 50 h, 72 h, 100 h, 136 h, and 180 h, respectively. Kinetics of 2-picolinic acid degradation was described using the Andrews equation. The kinetic parameters were as follows: q_max = 3.81 h^?1, K_s = 83.10 mg/L, and K_i = 252.11 mg/L. During the biodegradation process, Z2 transformed 2-picolinic acid into a product which was identified as 6-hydroxy picolinic acid by UV–vis spectrometry, ¹H nuclear magnetic resonance spectroscopy, and mass spectrometry. 6-Hydroxy picolinic acid was then cleaved and mineralized with release of ammonia.     

Diatom taxa and assemblages for establishing nutrient criteria of lakes with anthropogenic hydrologic alteration

Stressor-response models offer guidance for concentration-based nutrient criteria in lakes under human intervention. Diatom-based statistics from biological responses were incorporated to derive taxon-specific and community-level change points (thresholds) of phosphorous and nitrogen in 77 Yangtze floodplain lakes. Diatom metrics relating with conductivity were adopted as response variables, since conductivity explained the maximum variation (38.1%) in diatom assemblages via Bootstrapped regression trees. Nonparametric change-point analysis and Threshold Indicator Taxa ANalysis showed threshold responses of diatom community structure at 0.05–0.08 mg TP/L in connected lakes and 0.02–0.04 mg TP/L in isolated lakes. Distinct community change points of sensitive diatoms occurred at 0.96–1.63 mg TN/L in connected lakes and 0.52–0.63 mg TN/L in isolated lakes. Diatom community structures of tolerant taxa were substantially altered beyond 0.22–0.23 mg/L in connected lakes and 0.52–0.69 mg NO_x/L in isolated lakes. Hydrological river-lake connectivity differed significantly in ecological nutrient criteria with more TN/TP criteria and less NO_x criteria in connected lakes. Given the ecological significance and biological integrity, diatom-based statistics can provide more reliable change points (thresholds) for nutrient criteria than Chl a-nutrient relationships.     

Effect of different macrophytes in abating nitrogen from a synthetic wastewater

An experiment conducted in an unheated glasshouse from October 2006 to March 2008 studied the efficiency of different macrophytes in reducing NO₃-N and NH₄-N concentrations and loads in synthetic wastewaters. The experimental setup consisted of plastic tanks, filled with gravel and vegetated with Carex elata All., Juncus effusus L., Phragmites australis (Cav.) Trin., Typhoides arundinacea L. Moench (syn Phalaris arundinacea L.) var. picta and Typha latifolia L. There was also a control without vegetation. From January to July, a solution of 50–60 ppm of NH₄-N and NO₃-N was applied monthly; then the input concentration was doubled. The total load at the end of the experimental period was 70.4 g/m² of NO₃-N and 67.3 of NH₄-N. At the end of each month, water was discharged from the tanks and analysed to determine the two nitrogen forms. At the end of the experiment, 33 g/m² of total N (almost 24% of applied N) had disappeared in the control. Among species, the highest abatement was detected in T. latifolia (72 g/m², almost 52% of applied N) and the lowest in J. effusus (35%).A weekly chemical analysis in July showed that a large amount of NH₄-N quickly disappeared in all treatments, while NO₃-N only decreased in the vegetated tanks. In December, NH₄-N had similar dynamics, while NO₃-N increased.All water volumes entering and exiting the tanks were measured in order to evaluate evapotranspiration. T. latifolia showed the highest water consumption, reaching a cumulative value of above 1000 mm.At the end of the experiment, J. effusus presented the highest amount of nitrogen stored in the aerial parts (5.63 g/m²) and T. latifolia the lowest (1.92 g/m²).     

Photochemical NO release from nitrosyl RuII complexes with C-bound imidazoles

The series of nitrosyl complexes trans-[Ru(NH₃)₄L(NO)]Cl₃, L = caffeine, theophylline, imidazole and benzoimidazole in position trans to NO were prepared and their photochemical properties studied. All complexes showed nitric oxide (NO) release under light irradiation at 330–440 nm. Quantum yields for [Ru(NH₃)₄L(H₂O)]³⁺ formation (?_Ru(III)) were sensitive to the natures of L, λ_irr and pH. The major product of the irradiation of trans-[Ru(NH₃)₄L(NO⁺)]³⁺ is the trans-[Ru^III(NH₃)₄L(Cl)]²⁺ and NO as suggested by UV–Vis, electrochemical, and FTIR techniques.     

Nitrate removal and greenhouse gas production in a stream-bed denitrifying bioreactor

Denitrifying bioreactors are currently being tested as an option for treating nitrate (NO₃^?) contamination in groundwater and surface waters. However, a possible side effect of this technology is the production of greenhouse gases (GHG) including nitrous oxide (N₂O) and methane (CH₄). This study examines NO₃^? removal and GHG production in a stream-bed denitrifying bioreactor currently operating in Southern Ontario, Canada. The reactor contains organic carbon material (pine woodchips) intended to promote denitrification. Over a 1 year period, monthly averaged removal of influent (stream water) NO₃^? ranged from 18 to 100% (0.3–2.5 mg N L^?1). Concomitantly, reactor dissolved N₂O and CH₄ production, averaged 6.4 μg N L^?1 (2.4 mg N m^?2 d^?1), and 974 μg C L^?1 (297 mg C m^?2 d^?1) respectively, where production is calculated as the difference between inflow and effluent concentrations. Gas bubbles entrapped in sediments overlying the reactor had a composition ranging from 19 to 64% CH₄, 1 to 6% CO₂, and 0.5 to 2 ppmv N₂O; however, gas bubble emission rates were not quantified in this study. Dissolved N₂O production rates from the bioreactor were similar to emission rates reported for some agricultural croplands (e.g. 0.1–15 mg N m^?2 d^?1) and remained less than the highest rates observed in some N-polluted streams and rivers (e.g. 110 mg N m^?2 d^?1, Grand R., ON). Dissolved N₂O production represented only a small fraction (0.6%) of the observed NO₃^? removal over the monitoring period. Dissolved CH₄ production during summer months (up to 1236 mg C m^?2 d^?1), was higher than reported for some rivers and reservoirs (e.g. 6–66 mg C m^?2 d^?1) but remained lower than rates reported for some wastewater treatment facilities (e.g. sewage treatment plants and constructed wetlands, 19,500–38,000 mg C m^?2 d^?1).     

A nutrient biotic index (NBI) for use with benthic macroinvertebrate communities

Aquatic macroinvertebrates have been among the principal biological communities used for freshwater monitoring and assessment for several decades, but macroinvertebrate biomonitoring has not incorporated nutrient measures into assessment strategies. Two nutrient biotic indices were developed for benthic macroinvertebrate communities, one for total phosphorus (NBI-P), and one for nitrate (NBI-N). Weighted averaging was used to assess the distributions of 164 macroinvertebrate taxa across TP and NO₃⁻ gradients and to establish nutrient optima and subsequent nutrient tolerance values. Both the NBI-P and NBI-N were correlated with increasing mean TP and NO₃⁻ values (r = 0.68 and r = 0.57, respectively, p < 0.0001). A three-tiered scale of eutrophication for TP and NO₃⁻ (oligotrophic: ≤0.0175 mg/l TP, ≤0.24 mg/l NO₃⁻, mesotrophic: >0.0175 to ≤0.065 mg/l TP, >0.24 to ≤0.98 mg/l NO₃⁻, eutrophic: >0.065 mg/l TP, >0.98 mg/l NO₃⁻) was also established through cluster analysis of invertebrate communities using Bray–Curtis (quantitative) similarity. Significant differences (p < 0.0001) were detected between median NBI-P and NBI-N scores among the three trophic states. Therefore, the nutrient biotic indices (NBIs) appear to accurately reflect changes in stream trophic state. Multimetric water quality assessments were also used to identify thresholds of impairment among the three trophic states. Hodges-Lehman estimation indicated that the greatest change in assessment results occurred between the mesotrophic and eutrophic states. The eutrophic state also represented the highest percentage of overall impairment. Therefore, the suggested threshold for nutrient impairment is the boundary between mesotrophic and eutrophic (0.065 mg/l TP and 0.98 mg/l NO₃⁻). The corresponding NBI-P score (6.1) and NBI-N score (6.0) for this threshold incorporate predictive capabilities into the NBIs. The NBI and index score thresholds of impairment will provide monitoring programs with a robust measure of stream nutrient status and serve as a useful tool in enforcing regional nutrient criteria.     

Application of chemical precipitation and membrane bioreactor hybrid process for piggery wastewater treatment

This study was conducted to investigate the chemical precipitation (CP) and membrane bioreactor (MBR) hybrid process for the treatment of piggery wastewater. Average removal efficiencies for BOD, COD and turbidity in CP process were 64.3%, 77.3% and 96.4%, respectively. CP process had a moderate effect on NH₃–N removal (40.4%) which improved up to 98.2% mainly due to nitrification and filtration processes in MBR. The average removal efficiencies of BOD, COD and turbidity in MBR were 99.5%, 99.4% and 99.8%, respectively. Monod equation was used to explain the microbial activities in terms of specific growth rate. The specific growth rate of bacteria in aeration tank (N-batch) and anoxic tank (D-batch) were 0.013 and 0.005 d^?1 with a biomass yield of 0.78 and 0.43 mg MLSS produced/mg COD utilized, respectively. Microorganisms from the N-batch and D-batch showed a low-level of nitrifying and moderate-level of denitrifying capabilities which were 1.08 mg NH₃–N/(g MLVSS.h) and 2.82 mg NO₃–N/(g MLVSS.h), respectively. Carbohydrates were the main component in extracellular polymeric substance (EPS) compounds that could be attached to the membrane surface easily and led to membrane biofouling. The increase of MLSS, EPS and sludge viscosity concentration, decrease of sludge floc size and incomplete chemical cleaning procedure resulted in the increase of membrane resistance. Total membrane resistance increased from 3.19 × 10¹² m^?1 to 5.43 × 10¹⁴ m^?1.     

Availability of N and S affect nutrient acquisition efficiencies differently by Trifolium repens and Lolium perenne when grown in monoculture or in mixture

Sulphur (S) deficiency is recognized as a limiting factor for crop production in many regions in the world. In grasslands, S availability has been shown to alter the biomass production of Trifolium repens and Lolium perenne and their specific interactions. To establish the role of N and S availabilities on the competitive interaction for these minerals by T. repens and L. perenne when grown together, two S rates (0 and 30 kg S ha^?1) combined with three N rates (0, 50 and 180 kg N ha^?1) were investigated in a cut/regrowth experiment over a period of 4 months under glasshouse conditions. N was applied as ¹⁵NH₄ ¹⁵NO₃ to determine their actual N fertilizer recovery in the harvested fraction of the shoot. S yields were used to estimate their apparent S fertilizer recovery. At final harvest, N reserves of T. repens stolons were analyzed to estimate their implication in the regrowth process. In monoculture and in both cuts (1 and 2), N benefited both species by increasing their N and S yields. S benefited only T. repens. In mixture, at cut 1, L. perenne behaved as a better competitor than T. repens thanks to N, while at cut 2, T. repens dominated the community thanks to strong positive S effect. N recovery of L. perenne grown in mixture was greatly improved by S supply. For T. repens, S enhanced its ability to fix N₂ and improved the accumulation of soluble proteins in its stolons. It is clear that the N:S ratio of soil may affect the functionality of grassland plant communities and their structure. Results suggest that (i) the limitations in the availability of soil S could restrict leguminous species growth in high N soil conditions, and (ii) the modulation of S level could be used as a tool to modify the composition of grassland communities.     

Nitrate removal from three different effluents using large-scale denitrification beds

Simple technologies that remove nitrate from effluents and other point discharges need to be developed to reduce pollution of receiving waters. Denitrification beds are lined containers filled with organic carbon (typically wood chip or coarse sawdust) and are a technology that is proving promising. Water containing NO₃^? (treated effluent or agricultural drainage) is passed through the bed and the wood chips act as an energy source for denitrifying bacteria that convert NO₃^? to N gases. There are few data on the efficiency of NO₃ removal in large-scale beds. We report here NO₃^? removal results from three large denitrification beds with volumes of 83, 294, and 1320 m³ treating dairy shed effluent, treated domestic effluent and glasshouse effluent, respectively. Nitrate was nearly completely removed from the dairy shed effluent (annual load of 31 kg N) and domestic effluent (annual load 365 kg N). In these beds, NO₃^? removal, presumably by denitrification, was limited by NO₃^? concentration. However, the bed treating glasshouse effluent was overwhelmed by very high NO₃^? concentration (about 250 g N m^?3) and high flow rates (about 150 m³ d^?1) but still reduced NO₃^? concentration to about 150 g N m^?3. For this bed, long-term NO₃^? removal was between 5 and 10 g N m^?3 of bed material when NO₃^? was non-limiting and was similar to rates reported for other smaller denitrification beds. As expected, organic N, ammonium and phosphorus were not removed from any of the effluents following passage through the beds. Our results suggest that denitrification beds are a relatively inexpensive system to construct and operate, and are suitable for final treatment of a range of NO₃^?-laden effluents.     

Removal of nutrients from wastewater with Canna indica L. under different vertical-flow constructed wetland conditions

Constructed wetlands are becoming increasingly popular worldwide for removing contaminants from domestic wastewater. This study investigated the removal efficiency of nitrogen (N) and phosphorus (P) from wastewater with the simulated vertical-flow constructed wetlands (VFCWs) under three different substrates (i.e., BFAS or blast furnace artificial slag, CBAS or coal burn artificial slag, and MSAS or midsized sand artificial slag), hydraulic loading rates (i.e., 7, 14, and 21 cm d^?1), and wetland operational periods (0.5, 1, and 2 years) as well as with and without planting Canna indica L. The wastewater was collected from the campus of South China Agricultural University, Guangzhou, China. Results show that the percent removal of total P (TP) and ammonium N (NH₄⁺-N) by the substrates was BFAS > CBAS > MSAS due to the high contents of Ca and Al in substrate BFAS. In contrast, the percent removal of total N (TN) by the substrates was CBAS > MSAS > BFAS due to the complicated nitrification/denitrification processes. The percent removal of nutrients by all of the substrates was TP > NH₄⁺-N > TN. About 10% more TN was removed from the wastewater after planting Canna indica L. A lower hydraulic loading rate or longer hydraulic retention time (HRT) resulted in a higher removal of TP, NH₄⁺-N, and TN because of more contacts and interactions among nutrients, substrates, and roots under the longer HRT. Removal of NO₃^?N from the simulated VFCWs is a complex process. A high concentration of NO₃^?N in the effluent was observed under the high hydraulic loading rate because more NH₄⁺-N and oxygen were available for nitrification and a shorter HRT was unfavorable for denitrification. In general, a longer operational period had a highest removal rate for nutrients in the VFCWs.     

Purification,kinetic and thermodynamic characterization of soluble acid invertase from sugarcane (Saccharum officinarum L.)

We report for the first time kinetic and thermodynamic properties of soluble acid invertase (SAI) of sugarcane (Saccharum officinarum L.) salt sensitive local cultivar CP 77-400 (CP-77). The SAI was purified to apparent homogeneity on FPLC system. The crude enzyme was about 13 fold purified and recovery of SAI was 35%. The invertase was monomeric in nature and its native molecular mass on gel filtration and subunit mass on SDS-PAGE was 28 kDa. SAI was highly acidic having an optimum pH lower than 2. The acidic limb was missing. Proton transfer (donation and receiving) during catalysis was controlled by the basic limb having a pKa of 2.4. Carboxyl groups were involved in proton transfer during catalysis. The kinetic constants for sucrose hydrolysis by SAI were determined to be: k_m = 55 mg ml^?1, k_cat = 21 s^?1, k_cat/k_m = 0.38, while the thermodynamic parameters were: ΔH* = 52.6 kJ mol^?1, ΔG* = 71.2 kJ mol^?1, ΔS* = ?57 J mol^?1 K^?1, ΔG*_E–S = 10.8 kJ mol^?1 and ΔG*_E–T = 2.6 kJ mol^?1. The kinetics and thermodynamics of irreversible thermal denaturation at various temperatures 53–63 °C were also determined. The half -life of SAI at 53 and 63 °C was 112 and 10 min, respectively. At 55 °C, surprisingly the half -life increased to twice that at 53 °C. ΔG*, ΔH* and ΔS* of irreversible thermal stability of SAI at 55 °C were 107.7 kJ mol^?1, 276.04 kJ mol^?1 and 513 J mol^?1K^?1, respectively.     

Identification and evaluation of nutrient limitation on periphyton growth in headwater streams in the Pawnee Nation,Oklahoma

The objective of the study was to identify nutrient impacts, if any, on stream periphyton growth in Black Bear Creek (north central Oklahoma) and its tributaries. Passive diffusion periphytometers were deployed at ten study sites within the Black Bear Creek basin to evaluate periphyton growth in response to nutrient enrichment. These sites were selected to represent a gradient of land uses, from predominantly agricultural to predominantly urban. Periphytometer treatments included phosphorus (P) (1.0 mg/L PO₄-P, n = 10), nitrogen (N) (10.0 mg/L NO₃-N, n = 10), N plus P (n = 10) and control (reverse osmosis-treated water, n = 10). Results indicated that average dissolved inorganic N (DIN, PQL = 0.04 mg/L) concentrations were significantly correlated (R² = 0.63, p < 0.01) with chlorophyll a production on the periphytometer control treatments in the Black Bear Creek basin. Periphytic growth was nutrient-limited (increased chlorophyll a was measured on nutrient-enriched growth media) at four of the ten sites sampled; two sites were limited by N and two sites were co-limited by both N and P. The lotic ecosystem trophic status index (LETSI), the ratio of C to N + P chlorophyll a, was calculated to compare treatment responses across sites. At nutrient-limited sites, LETSI was positively correlated to ambient DIN values (R² = 0.97, p < 0.01). However, some sites that were not nutrient-limited had ambient nutrient concentrations similar to sites with observed nutrient limitation, indicating other factors were limiting periphyton growth at those sites.     

Mass balance of nitrogen in constructed mangrove wetlands receiving ammonium-rich wastewater: Effects of tidal regime and carbon supply

A series of computer-controlled mangrove tide-tanks planted with Kandelia candel was constructed to investigate the removal and transformation of ammonium–nitrogen under two tidal regimes: (i) 12-h wet/12-h dry (long tidal regime) and (ii) 6-h wet/6-h dry/6-h wet/6-h dry daily (short tidal regime). All tanks were irrigated with NH₄Cl solution for nine water cycles (each cycle lasted for 5 weeks) at an amount of around 2.1 g NH₄Cl (equivalent to 0.52 g N) per tank per cycle. During the experiment, total Kjeldahl nitrogen (TKN), inorganic nitrogen (N) (NH₄⁺–, NO₂^?–, and NO₃^?–N) and carbon were completely removed by the mangrove system. The added NH₄⁺–N was not detected in tidal water or accumulated in sediment. The mass balance of nitrogen showed that the discharge of ammonium-rich wastewater to mangrove wetlands enhanced microbial nitrogen transformation, particularly nitrification and denitrification processes, with 15–30% of the total nitrogen inputs returned to atmosphere as N₂ gas. Growth of K. candel and macroalgae was stimulated by ammonium addition, and up to 3 and 7% of total N inputs were assimilated in plant and algal tissues, respectively. Constructed mangrove wetlands with short tidal regime had higher numbers of nitrifiers and significantly lower content of ammonium that those with long tidal regime. On the other hand, higher populations of denitrifiers and lower nitrate were found in mangroves with long tidal regime and with glucose addition.     

Proton production from nitrogen transformation drives stream export of base cations in acid-sensitive forested watersheds

The biogeochemical cycles of nitrogen (N) and base cations (BCs), (i.e., K⁺, Na⁺, Ca²⁺, and Mg²⁺), play critical roles in plant nutrition and ecosystem function. Empirical correlations between large experimental N fertilizer additions to forest ecosystems and increased BCs loss in stream water are well demonstrated, but the mechanisms driving this coupling remain poorly understood. We hypothesized that protons generated through N transformation (PPR_N)—quantified as the balance of NH₄⁺ (H⁺ source) and NO₃⁻ (H⁺ sink) in precipitation versus the stream output will impact BCs loss in acid-sensitive ecosystems. To test this hypothesis, we monitored precipitation input and stream export of inorganic N and BCs for three years in an acid-sensitive forested watershed in a granite area of subtropical China. We found the precipitation input of inorganic N (17.71 kg N ha⁻¹ year⁻¹ with 54% as NH₄⁺–N) was considerably higher than stream exported inorganic N (5.99 kg N ha⁻¹ year⁻¹ with 83% as NO₃⁻–N), making the watershed a net N sink. The stream export of BCs (151, 1518, 851, and 252 mol ha⁻¹ year⁻¹ for K⁺, Na⁺, Ca²⁺, and Mg²⁺, respectively) was positively correlated (r = 0.80, 0.90, 0.84, and 0.84 for K⁺, Na⁺, Ca²⁺, and Mg²⁺ on a monthly scale, respectively, P < 0.001, n = 36) with PPR_N (389 mol ha⁻¹ year⁻¹) over the three years, suggesting that PPR_N drives loss of BCs in the acid-sensitive ecosystem. A global meta-analysis of 15 watershed studies from non-calcareous ecosystems further supports this hypothesis by showing a similarly strong correlation between ∑BCs output and PPR_N (r = 0.89, P < 0.001, n = 15), in spite of the pronounced differences in environmental settings. Collectively, our results suggest that N transformations rather than anions (NO₃⁻ and/or SO₄²⁻) leaching specifically, are an important mediator of BCs loss in acid-senstive ecosystems. Our study provides the first definitive evidence that the chronic N deposition and subsequent transformation within the watershed drive stream export of BCs through proton production in acid-sensitive ecosystems, irrespective of their current relatively high N retention. Our findings suggest the N-transformation-based proton production can be used as an indicator of watershed outflow quality in the acid-sensitive ecosystems.     

The effect of molecular packing on the occurrence of spin crossover phenomena in one-dimensional Fe(II)-bis-Schiff base complexes

Two new one-dimensional Fe(II)-bis-Schiff base complexes, [Fe(L1)(pyz)] · CH₂Cl₂ (1) and [Fe(L2)(pyz)] · 2CH₂Cl₂ (2) (H₂L1 = bis(O-vanillin)-O-phenylenediimine, H₂L2 = bis(O-vanillin)-2,3-naphthalenediimine, pyz = pyrazine) are reported with their crystal structures and magnetic property. Compound 1 shows a two-step SCO behavior while 2 shows HS at all the temperature range measured. Although the extension of aromatic moiety from benzene (L1) to naphthalene (L2) was introduced for the purpose of strengthening the cooperativity, it leads to the absence of SCO, due to the unanticipated π–π interaction, which leads to the longer Fe–N bond lengths and a weak ligand field around Fe(II) ion.     

The effects of NH4+ and NO3− on growth,resource allocation and nitrogen uptake kinetics of Phragmites australis and Glyceria maxima

The effects of NH₄⁺ or NO₃⁻ on growth, resource allocation and nitrogen (N) uptake kinetics of two common helophytes Phragmites australis (Cav.) Trin. ex Steudel and Glyceria maxima (Hartm.) Holmb. were studied in semi steady-state hydroponic cultures. At a steady-state nitrogen availability of 34 μM the growth rate of Phragmites was not affected by the N form (mean RGR = 35.4 mg g⁻¹ d⁻¹), whereas the growth rate of Glyceria was 16% higher in NH₄⁺-N cultures than in NO₃⁻-N cultures (mean = 66.7 and 57.4 mg g⁻¹ d⁻¹ of NH₄⁺ and NO₃⁻ treated plants, respectively). Phragmites and Glyceria had higher S/R ratio in NH₄⁺ cultures than in NO₃⁻ cultures, 123.5 and 129.7%, respectively.Species differed in the nitrogen utilisation. In Glyceria, the relative tissue N content was higher than in Phragmites and was increased in NH₄⁺ treated plants by 16%. The tissue NH₄⁺ concentration (mean = 1.6 μmol g fresh wt⁻¹) was not affected by N treatment, whereas NO₃⁻ contents were higher in NO₃⁻ (mean = 1.5 μmol g fresh wt⁻¹) than in NH₄⁺ (mean = 0.4 μmol g fresh wt⁻¹) treated plants. In Phragmites, NH₄⁺ (mean = 1.6 μmol g fresh wt⁻¹) and NO₃⁻ (mean = 0.2 μmol g fresh wt⁻¹) contents were not affected by the N regime. Species did not differ in NH₄⁺ (mean = 56.5 μmol g⁻¹ root dry wt h⁻¹) and NO₃⁻ (mean = 34.5 μmol g⁻¹ root dry wt h⁻¹) maximum uptake rates (V_max), and V_max for NH₄⁺ uptake was not affected by N treatment. The uptake rate of NO₃⁻ was low in NH₄⁺ treated plants, and an induction phase for NO₃⁻ was observed in NH₄⁺ treated Phragmites but not in Glyceria. Phragmites had low K_m (mean = 4.5 μM) and high affinity (10.3 l g⁻¹ root dry wt h⁻¹) for both ions compared to Glyceria (K_m = 6.3 μM, affinity = 8.0 l g⁻¹ root dry wt h⁻¹). The results showed different plasticity of Phragmites and Glyceria toward N source. The positive response to NH₄⁺-N source may participates in the observed success of Glyceria at NH₄⁺ rich sites, although other factors have to be considered. Higher plasticity of Phragmites toward low nutrient availability may favour this species at oligotrophic sites.     

Synthesis,crystal structure and magnetic properties of the spin crossover system [Fe(pq)3]2+

Three new compounds formulated (ClO₄)₂[Fe(pq)₃] (1), (BF₄)₂[Fe(pq)₃] · EtOH (2) and {(ClO₄)[MnCr(C₂O₄)₃][Fe(pq)₂(H₂O)₂]} (3), where pq is 2,2′-pyridylquinoline, have been synthesised and characterised. Despite the different crystal packing exhibited by 1 and 2, the cationic species [Fe(pq)₃]²⁺ are structurally quite similar. At 293 K, the Fe–N bond lengths are characteristic of the iron(II) in the high-spin state. In contrast to 1, 2 undergoes a continuous spin transition. Indeed, at 95 K its structure experiences a noticeable change in the Fe–N bonds and angles, i.e. the Fe–N bonds shorten by 0.194 Å on the average. The magnetic behaviour confirms that 1 is fully high-spin in the 4–300 K temperature range while 2 shows a spin transition centred at T_1/2 = 150 K. The corresponding enthalpy, entropy and interaction parameter are ΔH = 7.49 kJ mol^?1, ΔS = 50 J K^?1 mol^?1and Γ = 1.35 kJ mol^?1. Compound 3 has been obtained as a microcrystalline powder. The magnetic properties of 3 point at the occurrence of ferromagnetic coupling below 100 K and the onset of a ferromagnetic ordering below 10 K (Weiss constant equal to 6.8 K). The Mössbauer spectra of 3 show the occurrence of a magnetic order at T ? 4.2 K.