Relation between solid phase speciation and oral/lung bioaccessibility of metal(loid)s polluted soils in inhabited area: Contribution of synchrotron-based experiment.

The presence of contaminated sites/soils in or near cities can pose significant risks to public health. The city of Viviez (France) was taken in reference site bears significant industrial responsibility, particularly in zinc metallurgy, with the presence of a now rehabilitated smelter. This has led to soil contamination by zinc (Zn), lead (Pb), arsenic (As), and cadmium (Cd), with concentrations reaching up to 4856 mg kg-1, 1739 mg kg-1, 195 mg kg-1, and 110 mg kg-1, respectively. The aim of this study is to comprehend the contamination patterns of the site post-rehabilitation, the geochemical behavior of each element, and their speciation (analyzed through BCR, XRD, and XANES) in relation to associated health risks due to metals accessibility for oral ingestion and inhalation by the local population. The findings revealed that elements inducing health risks were not necessarily those with the highest metal contents. All results are discussed in terms of the relationship between element speciation, stability of bearing phases, and their behavior in different media. XANES is an important tool to determine and estimate the Pb-bearing phases in garden soils, as well as the As speciation, which consist of Pb-goethite, anglesite, and Pb-humate, with variations in proportions (the main phases being 66 %, 12 % and 22 % for Pb-goethite, anglesite, and Pb-humate, respectively) whereas As-bearing phase are As(V)-rich ferrihydrite-like. A new aspect lies in the detailed characterization of solid phases before and after bioaccessibility tests, to qualify and quantify the bearing phases involved in the mobility of metallic elements to understand the bioaccessibility behavior. Ultimately, the health risk associated with exposure to inhabitants, in terms of particle ingestion and inhalation, was assessed. Only ingestion-related risk was deemed unacceptable due to the levels of As and Pb.

A review: Biological technologies for nitrogen monoxide abatement.

Nitrogen oxides (NOx), including nitrogen monoxide (NO) and nitrogen dioxide (NO2), are among the most important global atmospheric pollutants because they have a negative impact on human respiratory health, animals, and the environment through the greenhouse effect and ozone layer destruction. NOx compounds are predominantly generated by anthropogenic activities, which involve combustion processes such as energy production, transportation, and industrial activities. The most widely used alternatives for NOx abatement on an industrial scale are selective catalytic and non-catalytic reductions; however, these alternatives have high costs when treating large air flows with low pollutant concentrations, and most of these methods generate residues that require further treatment. Therefore, biotechnologies that are normally used for wastewater treatment (based on nitrification, denitrification, anammox, microalgae, and combinations of these) are being investigated for flue gas treatment. Most of such investigations have focused on chemical absorption and biological reduction (CABR) systems using different equipment configurations, such as biofilters, rotating reactors, or membrane reactors. This review summarizes the current state of these biotechnologies available for NOx treatment, discusses and compares the use of different microorganisms, and analyzes the experimental performance of bioreactors used for NOx emission control, both at the laboratory scale and in industrial settings, to provide an overview of proven technical solutions and biotechnologies for NOx treatment. Additionally, a comparative assessment of the advantages and disadvantages is performed, and special challenges for biological technologies for NO abatement are presented.

Chlorine Concentration Modelling and Supervision in Water Distribution Systems.

The quality of the drinking water distributed through the networks has become the main concern of most operators. This work focuses on one of the most important variables of the drinking water distribution networks (WDN) that use disinfection, chlorine. This powerful disinfectant must be dosed carefully in order to reduce disinfection byproducts (DBPs). The literature demonstrates researchers' interest in modelling chlorine decay and using several different approaches. Nevertheless, the full-scale application of these models is far from being a reality in the supervision of water distribution networks. This paper combines the use of validated chlorine prediction models with an intensive study of a large amount of data and its influence on the model's parameters. These parameters are estimated and validated using data coming from the Supervisory Control and Data Acquisition (SCADA) software, a full-scale water distribution system, and using off-line analytics. The result is a powerful methodology for calibrating a chlorine decay model on-line which coherently evolves over time along with the significant variables that influence it.

Decreasing environmental impact of landfill leachate treatment by MBR, RO and EDR hybrid treatment.

A prototype pilot plant testing for a novel complete treatment strategy for landfill leachate aimed to decrease its environmental impact was studied. Pre-treatment of leachate was performed by means of a membrane biore-actor (MBR) decreasing inorganic carbon concentration by 92 ± 8% and achieving N removals of 85%. Suspended solids removal in the MBR >99.9% conditioned leachate for the next membrane step. Spiral-would reverse osmosis (RO) regenerated membranes were used to treat the MBR effluent. This RO unit achieved a global recovery of 84% along with operation and rejections of >95% for most of the analyzed compounds. Since RO permeate did not meet discharge standards, promising results were obtained after a second RO pass was applied. The RO brine produced was further concentrated by an electrodialysis reversal (EDR) unit, achieving an averaged recovery of 67% throughout the operation. The average recovery of the whole pilot plant system was >90%. The reduction of global brine volume together with the use of regenerated membranes are key to the environmental impact of the process and contribute to closing the loop of the circular economy. Life Cycle Assessment (LCA), performed according to ILCD Handbook guidelines, demonstrated that proposed new treatment had lower environmental impact than conventional treatments currently used in landfill facilities. Concretely, for the nine impact categories evaluated, the proposed treatment presented an average impact reduction of 93% compared to an advanced oxidation system and an average reduction of 26% when compared to a conventional RO treatment.

Hydrolysis and Methanogenesis in UASB-AnMBR Treating Municipal Wastewater Under Psychrophilic Conditions: Importance of Reactor Configuration and Inoculum.

Three upflow anaerobic sludge blanket (UASB) pilot scale reactors with different configurations and inocula: flocculent biomass (F-UASB), flocculent biomass and membrane solids separation (F-AnMBR) and granular biomass and membrane solids separation (G-AnMBR) were operated to compare start-up, solids hydrolysis and effluent quality. The parallel operation of UASBs with these different configurations at low temperatures (9.7 ± 2.4°C) and the low COD content (sCOD 54.1 ± 10.3 mg/L and pCOD 84.1 ± 48.5 mg/L), was novel and not previously reported. A quick start-up was observed for the three reactors and could be attributed to the previous acclimation of the seed sludge to the settled wastewater and to low temperatures. The results obtained for the first 45 days of operation showed that solids management was critical to reach a high effluent quality. Overall, the F-AnMBR showed higher rates of hydrolysis per solid removed (38%) among the three different UASB configurations tested. Flocculent biomass promoted slightly higher hydrolysis than granular biomass. The effluent quality obtained in the F-AnMBR was 38.0 ± 5.9 mg pCOD/L, 0.4 ± 0.9 mg sCOD/L, 9.9 ± 1.3 mg BOD5/L and <1 mg TSS/L. The microbial diversity of the biomass was also assessed. Bacteroidales and Clostridiales were the major bacterial fermenter orders detected and a relative high abundance of syntrophic bacteria was also detected. Additionally, an elevated abundance of sulfate reducing bacteria (SRB) was also identified and was attributed to the low COD/SO4 2- ratio of the wastewater (0.5). Also, the coexistence of acetoclastic and hydrogenotrophic methanogenesis was suggested. Overall this study demonstrates the suitability of UASB reactors coupled with membrane can achieve a high effluent quality when treating municipal wastewater under psychrophilic temperatures with F-AnMBR promoting slightly higher hydrolysis rates.

Investigating the relationship between speciation and oral/lung bioaccessibility of a highly contaminated tailing: contribution in health risk assessment.

Anthropogenic activities such as industrial, mining, or agricultural are the main sources of environmental contamination. One of the most problematic contaminations concerns metals and metalloids from mining activities. This contamination raises the question of the environmental risk induced and the spread of this pollution (geographical and trophic) and the associated health risk. The integrated, multi-analytical approach of this study conducted on the mining district of Cartagena-La Union (Murcia, Spain) as part of the Interreg SUDOE European project "Soil Take Care" aims to (i) precisely define the speciation of contaminants of interest (Zn, Pb, Cd, As), (ii) predict the environmental risk related to storage stability, and (iii) establish the link between the speciation of the bearing phases and the associated health risk. To do this, a representative zone in the Cartagena-La Union mining district close to the populations was chosen. A physic-chemical characterization of the samples was performed (pH, electrical conductivity, CEC, and total metal(loid) concentrations), and the mineralogy was determined using XRD and SEM-EDS. The environmental risk was highlighted from sequential BCR-type extractions and EN-12457 leaching tests. Finally, the health risk was defined using the PSF inhalation bioaccessibility test and UBM bioaccessibility protocol (based on an operational chemical methodology mimicking soil ingestion and its residence in the gastrointestinal tract of the human body). These analyses revealed 2 groups of samples with distinct behavior. The first group of samples presents relatively stable bearing phases, mainly found in the residual fraction (As and Pb), presenting only a low health risk (very low bioaccessible). The second group consists of Cd and/or Zn-bearing phases, mainly labile (resulting from dissolution/precipitation phenomena), while gastric bioaccessibility reaches more than 85%. Note that Pb, Cd, and Zn have the potential to cause non-carcinogenic risks to children and As and Pb present a carcinogenic risk for children and adults even if only the bioaccessible fraction is considered. It has therefore been shown that the meteoric alteration of the tailing induces a change in speciation leads to an increase in environmental and health risks. These results are essential because they highlight the need for an integrated approach in order to clearly highlight the presence of risks but also that this approach will allow a better understanding of the potential rehabilitation path of this site.

Coagulation-flocculation and moving bed biofilm reactor as pre-treatment for water recycling in the petrochemical industry.

Water recycling and reuse is of important value in water-using sectors like petrochemical industry. The aim of this research was to optimise the pre-treatment of petrochemical wastewater to undergo a further membrane treatment, with the final objective of water recycling within the same industry. Laboratory coagulation-flocculation tests prior to biological treatment were performed using Actiflo® Veolia commercial technology and an optimal coagulant dose of 30 mg/L ferric chloride was obtained. A bench-scale Moving Bed Biofilm Reactor (MBBR) system with two sequential reactors with working volumes of 5 L was filled with Z-carriers at 35% of their working volume. Organic loading rate (OLR) was varied from 0.2 to 3.25 kg/(m3 d) and the hydraulic retention time (HRT) ranged from 23.4 h to 4.5 h. High soluble chemical oxygen demand (sCOD) removals were obtained in stationary states (80-90%) and the calculated maximum sCOD that the system could degrade was 4.96 ±â€¯0.01 kg/(m3 d) at 23 ±â€¯2 °C. Changes in feed composition did not decrease sCOD removals showing that MBBR is a robust technology and the coagulation-flocculation step could be by-passed. Further removal of total suspended solids (TSS) and turbidity from the MBBR effluent would be required before a reverse osmosis (RO) step could be performed. A biofilm-forming genus, Haliscomenobacter spp., and an oil degrading genus Flavobacterium spp. were found in all the attached biomass samples. Acinetobacter spp. was the major bacterial genera found in suspended biomass. Proteobacteria and Bacteroidetes were the major phyla detected in the carrier samples while Proteobacteria the main one detected in the suspended biomass. The lack of fungal annotated sequences in databases led to a major proportion of fungal sequences being categorized as unclassified Fungi. The results obtained indicate that MBBR is an appropriate technology for hydrocarbon-degrading microorganism growth and, thus, for petrochemical wastewater pre-treatment for water regeneration.

Atmospheric dust characterisation in the mining district of Cartagena-La Unión, Spain: Air quality and health risks assessment.

Nowadays, air pollution has a major impact on the environment and human health. Owen gauges allow the sampling of atmospheric depositions in polluted sites for further characterisation. This paper shows the study of the air particles of an old mining zone in Cartagena-La Unión (South-east of Spain) in order to quantify their potential risk on human health. There were 4 strategic sites monitored: the main mining tailing (Avenque), the urban area (La Unión), an agricultural zone (formerly mining) and a site in the Mediterranean coast. Physico-chemical and mineralogical characterisation was applied to atmospheric fallouts. The granulometry revealed a dust particle size around 15 µm, with the coarsest particles in the urban area and the thinnest at the tailing site. XRD analyses showed the presence of quartz, carbonates, sulphides and sulphates. Observations with SEM-EDX confirmed chemical spectra and allowed us to classify the particles into well-crystallised minerals and heterogeneous dusts. Total metal content determination was carried out by ICP-MS analyses and results showed Zn, Pb, As and Cd fluxes (respectively 2549, 1275, 68 and 7 µg·m-2·d-1) exceeding the limit values set by European legislations in the mining area. The fluxes of Zn, Pb and As also exceed these standards in the urban area whereas the coastal zone only exceeds the thresholds in the case of As. Inhalation health risk (defined by US EPA, 2009) was quantified in the sites using total and bioaccessible metal contents of the dusts. Risk calculations using total metal content considering a residential scenario showed acceptable risk for all sites except for the mining tailing which presented non-acceptable cancer and hazard risk mainly due to the total As and Pb contents. When considering the bioaccessible fraction of As and Pb, the risk diminished to acceptable values, demonstrating the overestimation produced when using total metal contents.

Use of nitrogen and oxygen isotopes of dissolved nitrate to trace field-scale induced denitrification efficiency throughout an in-situ groundwater remediation strategy.

In the framework of the Life+ InSiTrate project, a pilot-plant was established to demonstrate the viability of inducing in-situ heterotrophic denitrification to remediate nitrate (NO3-)-polluted groundwater. Two injection wells supplied acetic acid by pulses to an alluvial aquifer for 22months. The monitoring was performed by regular sampling at three piezometers and two wells located downstream. In the present work, the pilot-plant monitoring samples were used to test the usefulness of the isotopic tools to evaluate the efficiency of the treatment. The laboratory microcosm experiments determined an isotopic fractionation (ε) for N-NO3- of -12.6‰ and for O-NO3- of -13.3‰. These ε15NNO3/N2 and ε18ONO3/N2 values were modelled by using a Rayleigh distillation equation to estimate the percentage of the induced denitrification at the pilot-plant while avoiding a possible interference from dilution due to non-polluted water inputs. In some of the field samples, the induced NO3- reduction was higher than 50% with respect to the background concentration. The field samples showed a reduced slope between δ18O-NO3- and δ15N-NO3- (0.7) compared to the laboratory experiments (1.1). This finding was attributed to the reoxidation of NO2- to NO3- during the treatment. The NO3- isotopic characterization also permitted the recognition of a mixture between the denitrified and partially or non-denitrified groundwater in one of the sampling points. Therefore, the isotopic tools demonstrated usefulness in assessing the implementation of the field-scale induced denitrification strategy.

Ecological screening indicators of stress and risk for the Llobregat river water.

The objective of this article is to develop and apply several simple and rough indicators for river aquatic ecosystems assessment in order to screen potential chemical stressors. Several indicators, based on toxicity (PNEC) and on legislation levels (EQS) have been developed. All these indicators are ratios that were calculated by using public and private data of concentrations of a large list of compounds during a period of five years, including metals and organic compounds in the lower part of the Llobregat river basin at the intake of the drinking water treatment plant. Additionally, new campaigns were executed for increasing the information available on the presence of compounds not routinely analyzed, such as some other pesticides and pharmaceuticals. In the case of inorganic pollutants, the indicators obtained in this river section showed significant risk especially for zinc, but also for copper, nickel and barium. For organic pollutants, the pesticides terbuthylazine, diazinon, 2-methyl-4-chlorophenoxyacetic (MCPA), and in a few cases, chlorpyrifos and lindane, also showed indexes above the threshold. Among the pharmaceuticals, the antibiotics clarithromycin and ciprofloxacin were the only ones with risk indicators adverse to ecosystems. The specific values of the indexes obtained rely on the quantity and quality of the data available, so their interpretation should take into account that some values can be high due to the use of too conservative toxicological information.

Model-based study of nitrite accumulation with OUR control in two continuous nitrifying activated sludge configurations.

Achievement of partial nitrification relies on the different characteristics of the microorganisms involved in the two steps of nitrification (AOB, ammonium oxidizing bacteria and NOB, nitrite oxidizing bacteria). Several configurations and conditions have been used to achieve partial nitrification taking into account their different responses in front of some environmental conditions like pH, temperature (T), dissolved oxygen (DO) and the inhibitory compounds free ammonia (FA) and free nitrous acid (FNA). This work is a theoretical study about the utilization of a control strategy based on controlling OUR by manipulating the influent flow-rate together with additional changes in T, pH or DO for achieving stable partial nitrification. Two different configurations were simulated. Configuration A consisted of three continuous stirred-tank reactors in series plus a settler, while configuration B consisted of a single reactor with the same total volume and a settler. The developed control system was shown as a good tool to achieve partial nitrification with both configurations. Nevertheless, configuration A showed better results and partial nitrification was obtained even under theoretically unfavourable conditions as T = 15 degrees Celsius, pH = 8.3 and DO = 3 mg O(2) L(-1).

Expert control for a stable operation of a partial nitrification system to treat highly concentrated ammonium wastewater.

This work presents the application of expert control strategies for a successful and stable operation of partial nitrification. A high-strength ammonium wastewater was treated in a continuous pilot plant with a configuration of three reactors in series plus a settler. The system was operated at mild temperature (around 25 degrees C) and at high sludge retention time to obtain a significant nitrifying biomass concentration. The implemented control system with expert supervisory rules provided a stable and robust operation of the partial nitrification system even when the pilot plant was subjected to several disturbances as change in influent concentration, failure of aeration in one reactor and operation with variable biomass concentration. The control system was based on local feedback control loops for dissolved oxygen and pH with proper setpoints for nitrite oxidizing bacteria (NOB) inhibition and an inflow control loop based on Oxygen Uptake Rate (OUR) measurements, which allowed working at the current maximum ammonium oxidation capacity. Two additional expert rules were implemented for automatically determine the required OUR setpoint in accordance with the biomass activity and to produce a fast load decrease when a system overload was detected.

Total and stable washout of nitrite oxidizing bacteria from a nitrifying continuous activated sludge system using automatic control based on Oxygen Uptake Rate measurements.

Partial nitrification (ammonium oxidation to nitrite) has gained a lot of interest among researchers in the last years because of its advantages with respect to complete nitrification (ammonium oxidation to nitrate): decrease of oxygen requirements for nitrification, reduction of COD demand and CO(2) emissions during denitrification and higher denitrification rate and lower biomass production during anoxic growth. In this study, an extremely high-strength ammonium wastewater (3000-4000mg NL(-1)) was treated in a continuous pilot plant with a configuration of three reactors in series plus a settler. The system was operated under the maximum possible volumetric nitrogen loading rate, at mild temperature (around 25 degrees C), with high sludge retention time (around 30d) and significant nitrifying biomass concentration (average of 1800+/-600mg VSSL(-1)). The implemented control loops transformed the system, which was operating with complete nitrification, into a continuous partial nitrification system. Nitrite oxidizing bacteria (NOB) washout was accomplished with local control loops for pH and dissolved oxygen (DO) with proper setpoints for NOB inhibition (pH=8.3 and DO=1.2-1.9mg O(2)L(-1)) and with an inflow control loop based on Oxygen Uptake Rate (OUR) measurements, which allowed working at the maximum ammonium oxidation capacity of the pilot plant in each moment. This operational strategy maximized the difference between ammonia oxidizing bacteria (AOB) and NOB growth rates, which is the key point to achieve a fast and stable NOB washout. The results showed a stable operation of the partial nitrification system during more than 100 days and NOB washout was corroborated with fluorescence in-situ hybridization (FISH) analysis.

Respirometric calibration and validation of a biological nitrite oxidation model including biomass growth and substrate inhibition.

The modelling of the nitrification process of high-strength ammonium wastewater must be designed to consider it as a two-step reaction with substrate inhibition. Consequently, kinetic and stoichiometric parameters of both steps are required. In this work, the second step in the nitrification process was studied: a biological nitrite oxidation model was formulated, calibrated and validated using only oxygen uptake rate (OUR) measurements. The model included biomass growth and substrate inhibition. First, the biomass yield coefficient for nitrite-oxidising biomass was determined. Then, a respirometric experiment with one nitrite pulse of 500 mg N-NO2- L(-1) was performed to estimate the rest of the model parameters. The practical identifiability study showed that the parameters were strongly correlated. Hence, a new experimental design consisting of two consecutive pulses and a delayed third one was designed to improve the parameter identifiability. Both experimental designs were compared using contour plots of the objective function and optimal experimental design criteria for parameter estimation. It was concluded that the parameter identifiability was improved with the new experimental design. Finally, the estimated parameters were validated and the pH effect on the inhibition coefficient was evaluated.