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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 - -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.)

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 ) 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 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 ) 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 -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 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.-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.)

Increasing knowledge of nitrate removal using denitrifying bioreactors has illustrated the usefulness of this management practice for treating discharge water from agricultural land uses. The objective of this study was to assess the viability of almond shell, chopped carob, olive bone, and citrus woodchip as carbon media for denitrification of brine with high nitrate load (EC ≈ 20 dS m -1 , NO 3 - -N concentration ≈ 65-80 mg NO 3 - -N L -1 ) in bioreactors. To the authors' knowledge, this is the first test of denitrifying brine using organic wastes as the carbon substrate, and the first use of these carbon media for that purpose. Nitrate removal efficiency and efficiency:cost ratio were considered. The results indicated that the best removal efficiency and cheapest cost were provided by citrus woodchip (3.02 ± 0.15 mg NO 3 - -N m -3 d -1 ) at a cost of ≈ 6€ m -3 , followed by almond shell (1.54 ± 0.20 mg NO 3 . Chopped carob and olive bone showed negligible nitrate removal in the brine; chopped carob generated acidic leachate with extremely high dissolved organic carbon, and olive bone resulted in a highly saline leachate. Of the four media tested, the results of this study indicated that citrus woodchip was the most suitable media for denitrification of the brine.- -N m -3 d -1 ) at a cost of ≈ 19€ m -3 . Chopped carob and olive bone showed negligible nitrate removal in the brine; chopped carob generated acidic leachate with extremely high dissolved organic carbon, and olive bone resulted in a highly saline leachate. Of the four media tested, the results of this study indicated that citrus woodchip was the most suitable media for denitrification of the brine.

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 &y& Elsevier]

Abstract: Salt marshes near urban, industrial and mining areas are often affected both by heavy metals and by eutrophic water. The aim of this study was to assess and evaluate the main processes involved in the decrease of nitrate concentration in pore water of mine wastes flooded with eutrophic water, considering the presence or absence of plant rhizhosphere. Basic (pH∼7.8) carbonated loam mine wastes and free-carbonated acidic (pH∼6.2) sandy-loam mine wastes were collected from polluted coastal salt marshes of SE Spain which regularly receive nutrient-enriched water. The wastes were put in pots and flooded for 15 weeks with eutrophic water (dissolved organic carbon ∼26mgL−1, PO4 3− ∼23mgL−1, NO3 − ∼180mgL−1). Three treatments were assayed for each type of waste: pots with Sarcocornia fruticosa, pots with Phragmites australis and unvegetated pots. Soluble organic carbon, nitrate, soluble Cd, Pb and Zn, pH and Eh were monitored. But the 2nd day of flooding, nitrate concentrations had decreased between 70% and 90% (equivalent to 1.01–1.12gN-NO3 − m−2 day−1) with respect to the content in the water used for flooding, except in unvegetated pots with acidic wastes. Denitrification was the main mechanism associated with the removal of nitrate. The role of vegetation in improving the rhizospheric environment was relevant in the acidic wastes because higher sand content, lower pH and higher soluble metal concentrations might strongly hinder microbial activity Hence, revegetation of salt marshes polluted by acidic sandy mining wastes might improve the capacity of this type of environment to act as a green filter against excessive nitrate contents flowing through them. [Copyright &y& Elsevier]