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To mitigate excess of nitrate-N (NO 3 - -N) derived from agricultural activity, constructed wetlands (CWs) are created to simulate natural removal mechanisms. Irrigated agricultural drainage water is commonly characterized by an organic carbon/nitrogen (C/N) imbalance, thus, C limitation constrains heterotrophic denitrification, the main biotic process implicated in NO 3 - -N removal in wetlands. We studied a pilot plant with three series (169 m 2 ) of hybrid CWs over the first two years of functioning to examine: i) the effect of adding different C-rich substrates (natural soil vs. biochar) to gravel on NO 3 - -N removal in a subsurface flow (Phase I), ii) the role of a second phase with a horizontal surface flow (Phase II) as a source of dissolved organic C (DOC), and its effect in a consecutive horizontal subsurface flow (Phase III) on NO 3 - -N removal, and iii) the contribution of each phase to global NO 3 - -N removal. Our results showed that the addition of a C-rich substrate to gravel had a positive effect on NO 3 - -N removal in Phase I, with mean efficiencies of 40% and 17% for soil and biochar addition, respectively, compared to only gravel (0.75%). In Phase II, the algae growth turned into a DOC concentration increase, but it did not enhance NO 3 - -N removal in Phase III. In series with C-rich substrate addition, the largest contribution to NO 3 - -N removal was found in Phase I. However, in series with only gravel, Phase II was the most effective on NO 3 - -N removal. Contribution of Phase III to NO 3 - -N removal was almost negligible., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Leachates from intensive agriculture containing high nitrate have been identified as a major cause of the severe eutrophication crisis that impacts Mar Menor (SE Spain), the largest hypersaline coastal lagoon in the Mediterranean basin. A best management practice for removing NO 3 - -N is denitrifying bioreactors. This is the first study to assess the efficiency of citrus woodchips bioreactors in treating agricultural leachates that flow to the Mar Menor via surface discharges. Denitrification capacity, woodchip degradation (by weight loss), formation of potentially harmful compounds, and greenhouse gas (GHG) emissions were assessed. Three bioreactors (6 m × 0.98 m x 1.2 m) filled with citrus woodchips (3 m 3  d -1 per bioreactor) through which the untreated ditch water over 1.5 years. Bioreactors were operated at 8 h, 16 h, and 24 h hydraulic residence time respectively, in each bioreactor. The main characteristics of the ditch water were: pH ≈ 7.5-8.0, electrical conductivity ≈ 5-8 dS m -1 , dissolved organic carbon ≈6-10 mg L -1 , and NO 3 - -N ≈ 22-45 mg L -1 . Bioreactors were highly efficient in reducing NO 3 - -N. The average R NO3 in effluents was for the complete experimental period 8 g N m -3 d -1 , 10.9 g N m -3 d -1 , and 12.6 g N m -3 d -1 for 8, 16 and 24 h residence time, respectively. Nitrate reduction efficiency was modulated by seasonal changes in temperature, with an increasing efficiency in warmer periods (maximum ≈ 85-90% for all hydraulic residence time) and decreasing in colder ones (minimum ≈ 12%, 23% and 41% for hydraulic residence time 8, 16 and 24 h respectively). Woodchips degradation was greatest during the first six months (average ≈ 29% weight loss) in the material above the water level, attributable to aerobic mineralization of the organic carbon, while weight loss was ≈11% in woodchip media continuously below the water level. Dissolved organic carbon, sulfide, ammonium, and soluble phosphorus concentrations in the effluents were mostly low, although some peaks in concentrations occurred. Design consideration must be taken to avoid environmental impacts due to the occasional presence of harmful compounds in the effluents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Phytomanagement is considered a suitable option in line with nature-based solutions to reduce environmental risks associated to metal(loid) mine tailings. We aimed at assessing the effectiveness of biochar from pruning trees combined with compost from urban solid refuse (USR) to ameliorate the conditions of barren acidic (pH ~5.5) metal(loid) mine tailing soils (total concentrations in mg kg -1 : As ~220, Cd ~40, Mn ~1800, Pb ~5300 and Zn ~8600) from Mediterranean semiarid areas and promote spontaneous plant colonization. Two months after amendment addition were enough to observe improvements in chemical and physico-chemical tailing soil properties (reduced acidity, salinity and water-soluble metals and increased organic carbon and nutrients content), which resulted in lowered ecotoxicity for the soil invertebrate Enchytraeus crypticus. Recalcitrant organic carbon provided by biochar remained in soil whereas labile organic compounds provided by USR were consumed over time. These improvements were consistent for at least one year and led to lower bulk density, higher water retention capacity and higher scores for microbial/functional-related parameters in the amended tailing soil. Spontaneous growth of native vegetation was favored with amendment addition, but adult plants of remarkable size were only found after three years. This highlights the existence of a time-lag between the positive effects of the amendment on tailing soil properties being observed and these improvements being translated into effective spontaneous plant colonization., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Woodchip bioreactors are widely known as a best management practice to reduce excess nitrate loads that are discharged with agricultural leachates. The aim of this study was to evaluate the performance of citrus woodchip bioreactors for denitrification of brine (electrical conductivity ≈ 17 mS cm -1 ) from groundwater desalination plants with high nitrate content (NO 3 - -N ≈ 48 mg L -1 ) in the Campo de Cartagena agricultural watershed, one of the main providers of horticultural products in Europe. The performance was evaluated relative to seasonal changes in temperature, dissolved organic carbon (DOC) provided by woodchips, hydraulic residence time (HRT) and woodchip aging. Bioreactors (capacity 1 m 3 ) operated for 2.5 years (121 weeks) in batch mode (24 h HRT) with three batches per week. Denitrification efficiency was modulated by DOC concentration, temperature, hydraulic residence time and the drying-rewetting cycles. High salinity of brine did not prevent nitrate removal from occurring. The high DOC availability (>25 mg C L -1 ) during the first ≈48 weeks resulted in high nitrate removal rate (>75%) and nitrate removal efficiency (until ≈ 25 g N m -3 d -1 ) regardless of temperature. Moreover, the high DOC contents in the effluents during this period may present environmental drawbacks. Denitrification was still high after 2.5 years (reaching ≈9.3 g N m -3 d -1 in week 121), but dependence on warm temperature became more apparent with woodchips aging from week ≈49 onwards. Nitrate removal efficiency was highest on the first weekly batch, immediately after woodchips had been unsaturated for four days. It was attributable to a flush of DOC produced by aerobic microbial metabolism during drying that stimulated denitrification following re-saturation. Hence, alternance of drying-rewetting cycles is an operation practice that increase bioreactors nitrate removal performance., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This study aimed to assess the effectiveness of biochar from sewage sludge -BSS- and from pruning trees -BPT- (addition dose of 6% d.w.) to immobilise metals in acidic (pH ∼ 4.7) and basic (pH ∼ 7.4) mine soils under variable flooding conditions, and to determine biochar influence on plant (Sarcocornia fruticosa -Sf-) growth and metal uptake. BSS had lower pH (∼8.2 vs. ∼ 9.8), CaCO 3 (∼71 vs. ∼ 85 g kg -1 ), total organic carbon (∼354 vs. ∼ 656 g kg -1 ) and higher water soluble organic carbon (WSOC ∼ 0.15 vs ∼ 0.06 mg kg -1 ) than BPT. PVC columns (15 × 30 cm) were prepared with the following treatments (n = 4): 1) no Biochar-no Sf; 2) no Biochar-Sf; 3) BSS-no Sf; 4) BSS-Sf; 5) BPT-no Sf; 6) BPT-Sf. Changes in water table level (WL) were simulated for 303 days with tap water (upper 0-15 cm alternating flooding-drying conditions, lower 15-30 cm always underwater). The pH, redox potential (Eh), temperature and porewater WSOC, Zn, Cd and Pb concentrations were regularly measured, and plants were removed at the end and length, fresh weight and metal concentrations in tissues measured. In the basic soil, there were no consistent evidences that BSS and BPT were effective decreasing porewater metal concentrations and reducing metal uptake in plants. Sf contributed to mobilise Zn, and in less extent Cd, in the upper soil layer, regardless of the type of biochar, and this effect increased with aging. In the acidic soil, BSS and BPT were effective increasing the pH and decreasing porewater metals. BSS increased its efficiency with aging, which can be mainly attributable to the more reduced conditions that induced (lower Eh values) due to its higher WSOC content. Biochar was effective hindering metal mobilisation by Sf and reducing plant's metal uptake (e.g. reduction in roots: ∼7 fold for Zn, ∼19-fold for Cd and ∼ 2-fold for Pb). BSS was more effective promoting Sf growth (fresh weight) than BPT. Therefore, in relation with the use of biochar from sewage sludge and from pruning trees as soil amendments under flooding-non flooding conditions, we can conclude that it can be a useful option in acidic mine soils for decreasing water soluble metals and improving plant growth. However, in basic mine soils, we have no evidences to support the advantages of using these two types of biochar as amendments. Hence, the use of biochar in metal-polluted wetlands has environmental implications that must be planned for each specific case in order to optimize the positive aspects (wetland as sinks of pollutants) and reduce the drawbacks (wetland as source of pollutants)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This study aimed to evaluate the response of salt marshes to pulses of PO 4 3- -enriched water, with and without the presence of Phragmites australis. A one-year mesocosms experiment was performed in simulated soil profiles (fine-textured surface layers and sandy subsurface layers) from a coastal salt marsh of the Mar Menor lagoon under alternating flooding-drying conditions with eutrophic water, under low (1.95 mg L -1 P-PO 4 3- ) and high (19.5 mg L -1 P-PO 4 3- ) P load, and with the presence/absence of Phragmites. The PO 4 3- concentrations in soil porewater and drainage water were regularly measured, and P accumulated in soils (including a fractionation procedure) and plants (roots, rhizomes, stems and leaves) were analyzed. The experimental mesocosms were highly effective in the removal of P from the eutrophic flooding water (>90% reduction of the P added to the system both in the soil pore water and drainage water), regardless of the nutrient load, the season of the year and the presence/absence of Phragmites. The soil was the main sink of the P added to the system, while Phragmites had a minor role in P removal. The biomass of Phragmites accumulated ∼27% of the P added with the flooding water in the treatment with water of low P load while ∼12% of P in that of high P load; the rhizomes were the organs that contributed the most (∼67-72% of the total P retained by the plants). Ca/Mg compounds were the main contributors to the retention of P in the soil compartment, especially in the fine-textured surface soil layers (∼34-53% of the total P in the soil was present in this fraction). Phragmites favored the retention of P onto metal oxides (∼12% increase of the P retained in the metal oxides fraction in the treatment with water of high P load). Hence, the use of constructed wetlands to ameliorate the negative impacts of P-enriched waters in the Mar Menor lagoon and similar areas is recommended. We propose the incorporation of fine-textured carbonated materials, with high content of Ca/Mg compounds, and the use of Phragmites to favor the retention of P by these systems., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Wetlands are highly effective systems in removing large amounts of N from waters, preventing eutrophication processes. However, when wetlands are polluted by metal-mine wastes their capacity to act as green filters may be diminished. The objective of this study was to evaluate the effect of liming and plants (Sarcocornia fruticosa and Phragmites australis) on the removal of NO3(-) from eutrophic water in slightly acidic, wetland soils polluted by metal-mine wastes. Simulated soil profiles were constructed and six treatments were assayed: (1) no liming + no plant, (2) no liming + S. fruticosa, (3) no liming + P. australis, (4) liming + no plant, (5) liming + S. fruticosa and (6) liming + P. australis. Three horizons were differentiated: A (never under water), C1 (alternating flooding-drying conditions) and C2 (always under water). The eutrophic water used to flood the soil profiles was enriched in N and organic carbon (pH ~ 7.5, electrical conductivity ~ 11 dS m(-1), NO3(-) ~ 234 mg L(-1) and dissolved organic carbon ~ 106 mg L(-1)). The pH, Eh and concentrations of dissolved organic carbon (DOC), N-NO3(-) and N-NH4(+) were measured regularly for 18 weeks. Liming stimulated the growth of plants, especially for S. fruticosa (20-fold more plant biomass than without liming), increased the soil pH and favoured the decline of the Eh values, enhancing the removal of NO3(-) via denitrification. Of all the treatments assayed, liming + S. fruticosa was the only treatment that removed almost completely the high concentration of NO3(-) from the eutrophic flooding water, reaching ~1 mg L(-1) N-NO3(-) at the end of the experiment, at all depths. The higher content of DOC in the pore water of this treatment could explain this behaviour, since more labile carbon was available to the soil microorganisms in the rhizosphere, favouring NO3(-) removal through denitrification processes. However, the treatment liming + P. australis (2-fold more plant biomass that without liming) did not remove completely the high concentrations of NO3(-) from the eutrophic water, except in the C2 horizon - which was permanently under water. Hence, our results show that the effectiveness of liming, regarding the removal of NO3(-) from eutrophic flooding water in wetland soils polluted by metal-mine wastes, depends on the presence of plants, their growth and the production of organic compounds in the rhizospheric environment., (Copyright © 2013 Elsevier Ltd. All rights reserved.)