The anaerobic biodegradation of emerging organic contaminants by horizontal subsurface flow constructed wetlands.

The horizontal subsurface flow constructed wetland (HFCW) is widely studied for the treatment of wastewater containing emerging organic contaminants (EOCs): pharmaceuticals, personal care products, and steroidal hormones. This study evaluates the performance of HFCW for the removal of these types of EOCs based on the data collected from peer-reviewed journal publications. In HFCW, anaerobic biodegradation is an important removal mechanism of EOCs besides their removal by the filter media (through sedimentation, adsorption, and precipitation) and plant uptake. The average removal efficiency of 18 selected EOCs ranged from 39% to 98%. The moderate to higher removal efficiency of 12 out of 18 selected EOCs in HFCW indicates the suitability of this type of constructed wetland (CW) for the treatment of wastewater containing these EOCs. The reasonably good removal (>50% in most of the cases) of these EOCs in HFCW might be due to the occurrence of anaerobic biodegradation as one of their major removal mechanisms in CWs. Although the effluent concentration of EOCs was substantially decreased after the treatment, the environmental risk posed by them was not fully reduced in most of the cases. For instance, estimated risk quotient of 11 out of 18 examined EOCs was extremely high for the effluent of HFCW.

Pseudomonas moraviensis subsp. stanleyae, a bacterial endophyte of hyperaccumulator Stanleya pinnata, is capable of efficient selenite reduction to elemental selenium under aerobic conditions.

AIMS: To identify bacteria with high selenium tolerance and reduction capacity for bioremediation of wastewater and nanoselenium particle production. METHODS AND RESULTS: A bacterial endophyte was isolated from the selenium hyperaccumulator Stanleya pinnata (Brassicaceae) growing on seleniferous soils in Colorado, USA. Based on fatty acid methyl ester analysis and multi-locus sequence analysis (MLSA) using 16S rRNA, gyrB, rpoB and rpoD genes, the isolate was identified as a subspecies of Pseudomonas moraviensis (97.3% nucleotide identity) and named P. moraviensis stanleyae. The isolate exhibited extreme tolerance to SeO3(2-) (up to 120 mmol l(-1)) and SeO4(2-) (>150 mmol l(-1)). Selenium oxyanion removal from growth medium was measured by microchip capillary electrophoresis (detection limit 95 nmol l(-1) for SeO3(2-) and 13 nmol l(-1) for SeO4(2-)). Within 48 h, P. moraviensis stanleyae aerobically reduced SeO3(2-) to red Se(0) from 10 mmol l(-1) to below the detection limit (removal rate 0.27 mmol h(-1) at 30 °C); anaerobic SeO3(2-) removal was slower. No SeO4(2-) removal was observed. Pseudomonas moraviensis stanleyae stimulated the growth of crop species Brassica juncea by 70% with no significant effect on Se accumulation. CONCLUSIONS: Pseudomonas moraviensis stanleyae can tolerate extreme levels of selenate and selenite and can deplete high levels of selenite under aerobic and anaerobic conditions. SIGNIFICANCE AND IMPACT OF THE STUDY: Pseudomonas moraviensis subsp. stanleyae may be useful for stimulating plant growth and for the treatment of Se-laden wastewater.

Phytotoxicity of citric acid and Tween® 80 for potential use as soil amendments in enhanced phytoremediation.

Enhanced phytoremediation adding biodegradable amendments like low molecular weight organic acids and surfactants is an interesting area of current research to overcome the limitation that represents low bioavailability of pollutants in soils. However, prior to their use in assisted phytoremediation, it is necessary to test if amendments per se exert any toxic effect to plants and to optimize their application mode. In this context, the present study assessed the effects of citric acid and Tween® 80 (polyethylene glycol sorbitan monooleate) on the development of alfalfa (Medicago sativa) plants, as influenced by their concentration and frequency of application, in order to evaluate the feasibility for their future use in enhanced phytoremediation of multi-contaminated soils. The results showed that citric acid negatively affected plant germination, while it did not have any significant effect on biomass or chlorophyll content. In turn, Tween® 80 did not affect plant germination and showed a trend to increase biomass, as well as it did not have any significant effect on chlorophyll levels. M. sativa appeared to tolerate citric acid and Tween® 80 at the tested concentrations, applied weekly. Consequently, citric acid and Tween® 80 could potentially be utilized to assist phytoremediation of contaminated soils vegetated with M. sativa.

Morphology, mineralogy, and solid-liquid phase separation characteristics of Cu and Zn precipitates produced with biogenic sulfide.

The morphology, mineralogy, and solid-liquid phase separation of the Cu and Zn precipitates formed with sulfide produced in a sulfate-reducing bioreactor were studied at pH 3, 5, and 7. The precipitates formed at pH 7 display faster settling rates, better dewaterability, and higher concentrations of settleable solids as compared to the precipitates formed at pH 3 and 5. These differences were linked to the agglomeration of the sulfidic precipitates and coprecipitation of the phosphate added to the bioreactor influent. The Cu and Zn quenched the intensity of the dissolved organic matter peaks identified by fluorescence-excitation emission matrix spectroscopy, suggesting a binding mechanism that decreases supersaturation, especially at pH 5. X-ray absorption fine structure spectroscopy analyses confirmed the precipitation of Zn-S as sphalerite and Cu-S as covellite in all samples, but also revealed the presence of Zn sorbed on hydroxyapatite. These analyses further showed that CuS structures remained amorphous regardless of the pH, whereas the ZnS structure was more organized at pH 5 as compared to the ZnS formed at pH 3 and 7, in agreement with the cubic sphalerite-type structures observed through scanning electron microscopy at pH 5.

Behaviour of different cementitious material formulations in sewer networks.

Sewer networks are subjected to degradation, including biodeterioration of materials, in the presence of biogenic sulfuric acid, leading to costly repairs. To ensure durable structures, it is essential to select the best adapted materials. Two cementitious materials based on ordinary Portland cement (OPC) or calcium aluminate cement (CAC), were subjected to biodeterioration in the headspace of an operating sewer network. After a few month OPC materials started to deteriorate whereas CAC materials were still intact. The better durability of CAC materials is due to the presence of alumina providing a combination of protective mechanisms. On-site environmental parameters were monitored and analysed in the context of the biological and chemical mechanisms involved in material degradation. These data will eventually feed into the development of a representative, reproducible and accelerated laboratory test.

Comparison of thermal and chemical enhanced recovery of DNAPL in saturated porous media: 2D tank pumping experiments and two-phase flow modelling.

Pumping experiments were performed in a 2D tank in order to estimate the recovery yield of pure heavy chlorinated organic compounds (DNAPL; dense non-aqueous phase liquids) by varying different parameters: permeability of the saturated zone, pumping flow rates, addition of surfactant and heating. Surfactant was added to decrease capillary forces involved in the entrapment of DNAPL in porous media while temperature was increased to reduce DNAPL viscosity (and hence increase its mobility). Chemical enhancement was performed with the addition of Sodium Dodecyl Benzene Sulfonate (SDBS) (at its Critical Micelle Concentration, to avoid DNAPL dissolution) and thermal enhancement was performed at 50 °C (to avoid DNAPL volatilization). The experiments were monitored with photography allowing, on the basis of image interpretation, to convert optical densities (OD) into water saturations (Sw). Image interpretations were compared with modelling results. The two-phase flow modelling was performed with the pressure-pressure formulation using capillary pressure and relative permeability functions based on the van Genuchten-Mualem equations. Measured volumes of DNAPL recovered as well as the displacement of the DNAPL-water interface (radius and height of the cone of depression) are consistent with the modelling results. Furthermore, chemical enhancement results in a significant increase in the recovery rates of DNAPL. The observed improvement in the recovery of DNAPL with chemical enhancement is due to the fact that: (i) the residual saturation inside the cone of depression is lower and (ii) the cone of depression radius and height increase. Thermal enhancement had no beneficial effect on DNAPL recovery rate or yield. This study shows that it is possible to accurately determine water and DNAPL saturations by image interpretation during pumping tests in a 2D tank in the laboratory. For field-scale applications, the two-phase flow model allows to determine remediation yields as well as the volumes of the cone of depression according to the different operating conditions.

Thermal and chemical enhanced recovery of heavy chlorinated organic compounds in saturated porous media: 1D cell drainage-imbibition experiments.

Chemical and thermal enhanced recovery of pure heavy chlorinated organic compounds (DNAPL; dense non-aqueous phase liquids) was investigated by using lab-scale 1D cells. Temperature was increased to reduce DNAPL viscosity (and hence increase its mobility), while surfactant was added to decrease capillary forces involved in the entrapment of DNAPL in porous media. Laboratory scale experiments, based on mass balance and indirect monitoring methods (i.e., permittivity, electrical resistivity and optical density), were conducted to quantify the effects of these enhancements. Heating the DNAPL up to 50 °C decreased its viscosity by a factor of two. The addition of a surfactant; i.e., Sodium Dodecyl Benzene Sulfonate (SDBS), at its Critical Micelle Concentration (to prevent DNAPL solubilization), decreased interfacial tensions by a factor of 12. Drainage-imbibition experiments performed in 1D cells provided retention curves (capillary pressure as a function of water saturation) of a two-phase (DNAPL-water) system in experimental glass bead porous media. The observed reduction of residual saturation (Srn) obtained with SDBS was 28% for 0.5 mm-diameter glass beads (GB) and 46% for 0.1 mm GB. No significant decrease in Sm was observed with thermal enhancement. The van Genuchten - Mualem model was found to satisfactorily reproduce the measured retention curves. Indirect measurements of water saturations (Sw) showed that: i. measured permittivities were very close to values modeled with the Complex Refractive Index Model (CRIM); ii. Archie's Law was less successful in reproducing measured electrical resistivities; iii. optical densities provide accurate estimations of Sw. At field scale, the combined monitoring of electrical resistivity (which provides a global picture) and permittivity (which yields locally precise but spatially limited information) is expected to significantly improve the collection of information on residual saturations Srn.

Leachate flush strategies for managing volatile fatty acids accumulation in leach-bed reactors.

In anaerobic leach-bed reactors (LBRs) co-digesting an easily- and a slowly-degradable substrate, the importance of the leachate flush both on extracting volatile fatty acids (VFAs) at the beginning of newly-started batches and on their consumption in mature reactors was tested. Regarding VFA extraction three leachate flush-rate conditions were studied: 0.5, 1 and 2Lkg-1TSd-1. Results showed that increasing the leachate flush-rate during the acidification phase is essential to increase degradation kinetics. After this initial phase, leachate injection is less important and the flush-rate could be reduced. The injection in mature reactors of leachate with an acetic acid concentration of 5 or 10gL-1 showed that for an optimized VFA consumption in LBRs, VFAs should be provided straight after the methane production peak in order to profit from a higher methanogenic activity, and every 6-7h to maintain a high biogas production rate.

Biological removal of selenate and ammonium by activated sludge in a sequencing batch reactor.

Wastewaters contaminated by both selenium and ammonium need to be treated prior to discharge into natural water bodies, but there are no studies on the simultaneous removal of selenium and ammonium. A sequencing batch reactor (SBR) was inoculated with activated sludge and operated for 90days. The highest ammonium removal efficiency achieved was 98%, while the total nitrogen removal was 75%. Nearly a complete chemical oxygen demand removal efficiency was attained after 16days of operation, whereas complete selenate removal was achieved only after 66days. The highest total Se removal efficiency was 97%. Batch experiments showed that the total Se in the aqueous phase decreased by 21% with increasing initial ammonium concentration from 50 to 100mgL-1. This study showed that SBR can remove both selenate and ammonium via, respectively, bioreduction and partial nitrification-denitrification and thus offer possibilities for treating selenium and ammonium contaminated effluents.

Mesophilic anaerobic digestion of several types of spent livestock bedding in a batch leach-bed reactor: substrate characterization and process performance.

Spent animal bedding is a valuable resource for green energy production in rural areas. The properties of six types of spent bedding collected from deep-litter stables, housing either sheeps, goats, horses or cows, were compared and their anaerobic digestion in a batch Leach-Bed Reactor (LBR) was assessed. Spent horse bedding, when compared to all the other types, appeared to differ the most due to a greater amount of straw added to the litter and a more frequent litter change. Total solids content appeared to vary significantly from one bedding type to another, with consequent impact on the methane produced from the raw substrate. However, all the types of spent bedding had similar VS/TS (82.3-88.9)%, a C/N well-suited to anaerobic digestion (20-28, except that of the horse, 42) and their BMPs were in a narrow range (192-239NmLCH4/gVS). The anaerobic digestion in each LBR was stable and the pH always remained higher than 6.6 regardless of the type of bedding. In contrast to all the other substrates, spent goat bedding showed a stronger acidification resulting in a methane production lag phase. Finally, spent bedding of different origins reached, on average, (89±11)% of their BMP after 60days of operation. This means that this waste is well-suited for treatment in LBRs and that this is a promising process to recover energy from dry agricultural waste.

Comparison of the mesophilic and thermophilic anaerobic digestion of spent cow bedding in leach-bed reactors.

Anaerobic digestion of spent cow bedding in batch leach-bed reactors (LBRs) was compared in mesophilic and thermophilic conditions for the first time. Results show that the use of thermophilic conditions enhanced only the degradation kinetics of easily-degradable matter during the first days of the digestion, whereas similar methane yields (80% of the Biomethane Potential) were reached after 42days at both temperatures. Therefore, the anaerobic digestion in LBRs of spent cow bedding, a substrate rich in slowly-degradable compounds, was not improved in term of methane production considering the overall digestion time. Moreover, the high initial biogas production rate in thermophilic reactors was found to significantly reduce the energetic performance of the cogeneration unit at industrial scale, leading to a 5.9% decrease in the annual electricity production when compared to a mesophilic one.

Citric acid- and Tween(®) 80-assisted phytoremediation of a co-contaminated soil: alfalfa (Medicago sativa L.) performance and remediation potential.

A pot experiment was designed to assess the phytoremediation potential of alfalfa (Medicago sativa L.) in a co-contaminated (i.e., heavy metals and petroleum hydrocarbons) soil and the influence of citric acid and Tween(®) 80 (polyethylene glycol sorbitan monooleate), applied individually and combined together, for their possible use in chemically assisted phytoremediation. The results showed that alfalfa plants could tolerate and grow in a co-contaminated soil. Over a 90-day experimental time, shoot and root biomass increased and negligible plant mortality occurred. Heavy metals were uptaken by alfalfa to a limited extent, mostly by plant roots, and their concentration in plant tissues were in the following order: Zn > Cu > Pb. Microbial population (alkane-degrading microorganisms) and activity (lipase enzyme) were enhanced in the presence of alfalfa with rhizosphere effects of 9.1 and 1.5, respectively, after 90 days. Soil amendments did not significantly enhance plant metal concentration or total uptake. In contrast, the combination of citric acid and Tween(®) 80 significantly improved alkane-degrading microorganisms (2.4-fold increase) and lipase activity (5.3-fold increase) in the rhizosphere of amended plants, after 30 days of experiment. This evidence supports a favorable response of alfalfa in terms of tolerance to a co-contaminated soil and improvement of rhizosphere microbial number and activity, additionally enhanced by the joint application of citric acid and Tween(®) 80, which could be promising for future phytoremediation applications.

Effect of heavy metal co-contaminants on selenite bioreduction by anaerobic granular sludge.

This study investigated bioreduction of selenite by anaerobic granular sludge in the presence of heavy metals and analyzed the fate of the bioreduced selenium and the heavy metals. Selenite bioreduction was not significantly inhibited in the presence of Pb(II) and Zn(II). More than 92% of 79 mg/L selenite was removed by bioreduction even in the presence of 150 mg/L of Pb(II) or 400mg/L of Zn(II). In contrast, only 65-48% selenite was bioreduced in the presence of 150-400 mg/L Cd(II). Formation of elemental selenium or selenide varied with heavy metal type and concentration. Notably, the majority of the bioreduced selenium (70-90% in the presence of Pb and Zn, 50-70% in the presence of Cd) and heavy metals (80-90% of Pb and Zn, 60-80% of Cd) were associated with the granular sludge. The results have implications in the treatment of selenium wastewaters and biogenesis of metal selenides.

Recovery of molybdenum, nickel and cobalt by precipitation from the acidic leachate of a mineral sludge.

The objective of this study was to investigate the recovery potential of molybdenum (Mo), nickel (Ni) and cobalt (Co) from synthetic and real acidic leachate of a mineral sludge from a metal recycling plant by sulfide precipitation. The operational parameters (metal sulfide (M/S) ratio 0.1-1, agitation speed 0-100 rpm, contact time 15-120 min and pH 1-5) were optimized in batch conditions on synthetic metal leachate (0.5 M HNO3, Mo = 101.6 mg L(-1), Ni = 70.8 mg L(-1), Co = 27.1 mg L(-1)) with a 0.1 M Na2S solution. Additionally, recovery of the target metals was theoretically simulated with a chemical equilibrium model (Visual MINTEQ 3.0). The optimized Na2S precipitation of metals from the synthetic leachate resulted in the potential selective recovery of Mo at pH 1 (98% by modeling, 95% experimental), after simultaneous precipitation of Ni and Co as sulfide at pH 4 (100% by modeling, 98% experimental). Metal precipitation from the real leachate (18 M H2SO4, Mo = 10,160 mg L(-1), Ni = 7,080 mg L(-1), Co = 2,710 mg L(-1)) was performed with 1 M Na2S, and resulted in a maximal Mo recovery at pH 2 (50%), while maximal recoveries of Ni and Co were observed at pH 4 (56% and 60%, respectively). Real leachate gave a lower metals recovery efficiency compared with synthetic leachate, which can be attributed to changes in the pH, nature of leachant, co-precipitation of Zn and competition for S(2-) ions.

Importance of organic amendment characteristics on bioremediation of PAH-contaminated soil.

This study investigates the importance of the organic matter characteristics of several organic amendments (i.e., buffalo manure, food and kitchen waste, fruit and vegetables waste, and activated sewage sludge) and their influence in the bioremediation of a polycyclic aromatic hydrocarbons (PAH)-contaminated soil. The removal of low molecular weights (LMW) and high molecular weights (HMW) PAHs was monitored in four bioremediation reactors and used as an indicator of the role of organic amendments in contaminant removal. The total initial concentration of LMW PAHs was 234 mg kg(-1) soil (dry weight), while the amount for HMW PAHs was 422 mg kg(-1) soil (dry weight). Monitoring of operational parameters and chemical analysis was performed during 20 weeks. The concentrations of LMW PAH residues in soil were significantly lower in reactors that displayed a mesophilic phase, i.e., 11 and 15 %, compared to reactors that displayed a thermophilic phase, i.e., 29 and 31 %. Residual HMW PAHs were up to five times higher compared to residual LMW PAHs, depending on the reactor. This demonstrated that the amount of added organic matter and macronutrients such as nitrogen and phosphorus, the biochemical organic compound classes (mostly soluble fraction and proteins), and the operational temperature are important factors affecting the overall efficiency of bioremediation. On that basis, this study shows that characterization of biochemical families could contribute to a better understanding of the effects of organic amendments and clarify their different efficiency during a bioremediation process of PAH-contaminated soil.

Comparative bioremediation of heavy metals and petroleum hydrocarbons co-contaminated soil by natural attenuation, phytoremediation, bioaugmentation and bioaugmentation-assisted phytoremediation.

Biological remediation technologies are an environmentally friendly approach for the treatment of polluted soils. This study evaluated through a pot experiment four bioremediation strategies: a) natural attenuation, b) phytoremediation with alfalfa (Medicago sativa L.), c) bioaugmentation with Pseudomonas aeruginosa and d) bioaugmentation-assisted phytoremediation, for the treatment of a co-contaminated soil presenting moderate levels of heavy metals (Cu, Pb and Zn at 87, 100 and 110mgkg(-1) DW, respectively) and petroleum hydrocarbons (3800mgkg(-1) DW). As demonstrated by plant biomass and selected physiological parameters alfalfa plants were able to tolerate and grow in the co-contaminated soil, especially when soil was inoculated with P. aeruginosa, which promoted plant growth (56% and 105% increase for shoots and roots, respectively) and appeared to alleviate plant stress. The content of heavy metals in alfalfa plants was limited and followed the order: Zn>Cu>Pb. Heavy metals were mainly concentrated in plant roots and were poorly translocated, favouring their stabilization in the root zone. Bioaugmentation of planted soil with P. aeruginosa generally led to a decrease of plant metal concentration and translocation. The highest degree of total petroleum hydrocarbon removal was obtained for bioaugmentation-assisted phytoremediation treatment (68%), followed by bioaugmentation (59%), phytoremediation (47%) and natural attenuation (37%). The results of this study demonstrated that the combined use of plant and bacteria was the most advantageous option for the treatment of the present co-contaminated soil, as compared to natural attenuation, bioaugmentation or phytoremediation applied alone.

Acid extraction of molybdenum, nickel and cobalt from mineral sludge generated by rainfall water at a metal recycling plant.

This study investigated the leaching yields of Mo, Ni and Co from a mineral sludge of a metal recycling plant generated by rainfalls. The investigated mineral sludge had a complex heterogeneous composition, consisting of particles of settled soil combined with metal-bearing particles (produced by catalysts, metallic oxides and battery recycling). The leaching potential of different leaching reagents (stand-alone strong acids (HNO3 (68%), H2SO4 (98%) and HCl (36%)) and acid mixtures (aqua regia (nitric + hydrochloric (1:3)), nitric + sulphuric (1:1) and nitric + sulphuric + hydrochloric (2:1:1)) was investigated at changing operational parameters (solid-liquid (S/L) ratio, leaching time and temperature), in order to select the leaching reagent which achieves the highest metal leaching yields. Sulphuric acid (98% H2SO4) was found to be the leachant with the highest metal leaching potential. The optimal leaching conditions were a three-stage successive leaching at 80 °C with a leaching time of 2 h and S/L ratio of 0.25 g L(-1). Under these conditions, the achieved mineral sludge sample leaching yields were 85.5%, 40.5% and 93.8% for Mo, Ni and Co, respectively. The higher metal leaching potential of H2SO4 in comparison with the other strong acids/acid mixtures is attributed to the fact that H2SO4 is a diacidic compound, thus it has more H(+) ions, resulting in its stronger oxidizing power and corrosiveness.

Fluidized-bed denitrification of mining water tolerates high nickel concentrations.

This study revealed that fluidized-bed denitrifying cultures tolerated soluble Ni concentrations up to 500 mg/L at 7-8 and 22°C. From 10 to 40 mg/L of feed Ni, denitrification resulted in complete nitrate and nitrite removal. The concomitant reduction of 30 mg/L of sulfate produced 10 mg/L of sulfide that precipitated nickel, resulting in soluble effluent Ni below 22 mg/L. At this stage, Dechloromonas species were the dominant denitrifying bacteria. From 60 to 500 mg/L of feed Ni, nickel remained in solution due to the inhibition of sulfate reduction. At soluble 60 mg/L of Ni, denitrification was partially inhibited prior to recover after 34 days of enrichment by other Ni-tolerant species (including Delftia, Zoogloea and Azospira) that supported Dechloromonas. Subsequently, the FBR cultures completely removed nitrate even at 500 mg/L of Ni. Visual Minteq speciation model predicted the formation of NiS, NiCO3 and Ni3(PO4)2, whilst only Ni3(PO4)2 was detected by XRD.

Fate of Trace Metals in Anaerobic Digestion.

A challenging, and largely uncharted, area of research in the field of anaerobic digestion science and technology is in understanding the roles of trace metals in enabling biogas production. This is a major knowledge gap and a multifaceted problem involving metal chemistry; physical interactions of metal and solids; microbiology; and technology optimization. Moreover, the fate of trace metals, and the chemical speciation and transport of trace metals in environments--often agricultural lands receiving discharge waters from anaerobic digestion processes--simultaneously represents challenges for environmental protection and opportunities to close process loops in anaerobic digestion.