RESUMO
We examined the temporal profiles of many organic micropollutants analysed in a sediment core sampled from a highly anthropized tributary of the Po River, the Lambro River. Analysed for extractable organic halogens (EOX), total petroleum hydrocarbons (C10-C40TPH), polycyclic aromatic hydrocarbons (PAHs), common legacy pollutants (DDTs, PCBs), halogenated flame retardants (PBDEs, DBDPE, TBBPA-bis, TCBPA, TBBPA, HBCDs), organotins (TBT, TPhT), antimicrobials (TCS, TCC), fragrances (AHTN, HHCB) and phthalates (DMP, DEP, DnBP, BBP, DEHP, DnOP), the dated sediment core revealed the historical record of 50 years of chemical contamination discharged into the Lambro and thereby the Po River. In this regard, the peak levels of PCBs and DDTs found in Lambro sediments were also identified in other sediment cores collected from the Po River prodelta in the Adriatic Sea, thus hundreds of kilometres downstream (Combi et al., 2020). The highest risk to aquatic organisms was associated with decades of high levels of C10-C40 TPH, PBDEs, PCBs, PAHs, DDTs, EOX, TCC, AHTN and DEHP, which in different periods of the contamination history, showed exceedances of guideline/threshold values. C10-C40 TPH and TCC, for example, were very high in the 1960s, whereas PCBs, DDTs, and PBDEs, peaked from the 1980s onward. The corresponding sums of PEC quotients ranged between 0.48 and 28.63, with a mean value (±SD) for the entire recording period of 10.62 ± 9.83. Environmental legislations and improved wastewater treatments were the main drivers of the recent downward trends observed for most of the chemicals investigated. Floods in turn resulted in macroscopic yet temporary improvements in the chemical quality of the tributary, conveying contaminated sediments into the Po River.
Assuntos
Dietilexilftalato , Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Bifenilos Policlorados/análise , Sedimentos Geológicos/química , Éteres Difenil Halogenados/análise , Monitoramento Ambiental , Poluentes Químicos da Água/análise , ItáliaRESUMO
In the last decades particular attention is being paid to the efficient and effective removal of compounds of emerging concern (CECs) present in wastewater before their eventual reuse or disposal. Several technologies have been developed for the degradation of CECs in aqueous matrix, in this regard advanced oxidation processes (AOPs) represent a nascent technological solution developed on a laboratory scale with applications on a prototype scale. The experimental evidences have shown that AOPs processes can oxidize numerous organic compounds in a much faster and more efficient way than that of the most common disinfection processes. The most common AOPs processes are those that involve the use of H2O2/UV, O3/UV, H2O2/O3, H2O2/O3/UV, Fenton and photo-Fenton. The aim of this work is to illustrate the results of a comparative LCA study of a laboratory scale UV-C photoreactor for the tertiary treatment of urban wastewater of three treatment systems (UV-C, UV-C + H2O2 e UV-C + TiO2). In particular, the specific objective is to evaluate, from an environmental point of view, an innovative advanced oxidation system based on nanostructures TiO2 immobilized on a stainless steel mesh. Compared to the UV-C photolysis reference system, the addition of hydrogen peroxide reduces the total environmental impact of the system by almost 75 %, while the use of the stainless-steel mesh coated by the nanostructures titanium dioxide reduces the UV-C environmental impact by 30 %. These results are due to the lower energy consumption of these last treatments compared to photolysis alone. The main impacts of the three systems are related to the electric power consumption of the centrifugal pump (63-64 %) and of the UV-C lamp (32-33 %). The LCA applied to these systems has shown that TiO2 assisted photocatalysis is not yet advantageous from an environmental point of view and that, therefore, the efficiency of the system needs to be improved.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Animais , Águas Residuárias/química , Peróxido de Hidrogênio/química , Poluentes Químicos da Água/análise , Raios Ultravioleta , Oxirredução , Estágios do Ciclo de Vida , Purificação da Água/métodosRESUMO
The fluctuation in the number of people in tourist areas affects the wastewater quality and quantity. Constructed wetlands (CWs) aim to simulate physical, chemical, and biological processes occurring in natural environments for wastewater treatment and are considered a sustainable system. The current study aimed at evaluating the effectiveness of in-vessel CWs for supporting the wastewaters treatment plants in periods of overloading. Such approach can be quickly implementable, economic, and the CWs can be fast regenerated in the framework of sustainable good practices. Three pilot scale CWs were prepared in as many containers layering 10 cm of gravel, 60 cm of sand and 10 cm of gravel, and placing pieces of giant reed rhizomes in the upper layers. The bottom of each CW had a tap, and CWs were irrigated with a real municipal sewage three times a week. Before each new irrigation, the tap was opened, and the effluent collected for determining gross parameters, elemental composition, and contaminants of emerging concern (CECs). CWs significantly reduced almost all gross parameters considered and half the CECs, except for a couple of metabolites of corresponding parental compounds. With regards to the potentially toxic elements, all reduced their concentration from the influents to the effluents. The results of this study were promising and highlighted good efficiency of constructed wetlands as pre-treatment of real municipal sewage to reduce the overloading of the wastewater treatment plant.
RESUMO
The irrigation with treated wastewater is among the main anthropogenic sources for the release of pharmaceuticals (PhACs) into the soils and their translocation into crops, with possible toxic and adverse effects on humans. The arbuscular mycorrhizal fungi (AMF) can be employed for the reduction of organic soil pollutants, even if their efficiency depends on the mycorrhizal fungi, the plant colonized, and the type and concentration of the contaminant. This study aimed to evaluate the uptake of PhACs from wastewaters of different qualities used for the irrigation of mycorrhizal artichoke plants, the presence in their edible parts and the role of the arbuscular mycorrhizal fungi. The research was carried out on artichoke plants not inoculated and inoculated with two different AMF and irrigated with treated wastewater (TW), groundwater (GW) or GW spiked with different and selected PhACs (SGW). The inocula were a crude inoculum of Septoglomus viscosum (MSE) and a commercial inoculum of Glomus intraradices and Glomus mosseae (MSY). The results of the present study showed that carbamazepine and fluconazole were found in the artichoke only with SGW irrigation. The mycorrhizal plants showed a reduction of the pharmaceutical's uptake, and within the AMF, MSE was more effective in preventing their absorption and translocation.
Assuntos
Cynara scolymus , Micorrizas , Poluentes do Solo , Humanos , Águas Residuárias , Solo , Plantas/microbiologia , Poluentes do Solo/análise , Preparações Farmacêuticas , Raízes de Plantas/químicaRESUMO
Endocrine disrupting compounds (EDCs) in the environment are considered a motif of concern, due to the widespread occurrence and potential adverse ecological and human health effects. The natural estrogen, 17ß-estradiol (E2), is frequently detected in receiving water bodies after not being efficiently removed in conventional wastewater treatment plants (WWTPs), promoting a negative impact for both the aquatic ecosystem and human health. In this study, the biodegradation of E2 by Rhodococcus sp. ED55, a bacterial strain isolated from sediments of a discharge point of WWTP in Coloane, Macau, was investigated. Rhodococcus sp. ED55 was able to completely degrade 5 mg/L of E2 in 4 h in a synthetic medium. A similar degradation pattern was observed when the bacterial strain was used in wastewater collected from a WWTP, where a significant improvement in the degradation of the compound occurred. The detection and identification of 17 metabolites was achieved by means of UPLC/ESI/HRMS, which proposed a degradation pathway of E2. The acute test with luminescent marine bacterium Aliivibrio fischeri revealed the elimination of the toxicity of the treated effluent and the standardized yeast estrogenic (S-YES) assay with the recombinant strain of Saccharomyces cerevisiae revealed a decrease in the estrogenic activity of wastewater samples after biodegradation.
Assuntos
Disruptores Endócrinos , Rhodococcus , Poluentes Químicos da Água , Ecossistema , Disruptores Endócrinos/análise , Estradiol/metabolismo , Estrogênios/metabolismo , Humanos , Redes e Vias Metabólicas , Rhodococcus/metabolismo , Eliminação de Resíduos Líquidos , Águas Residuárias , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidadeRESUMO
This study evaluated whether some chemical and microbial contaminants in treated sewage effluents from two wastewater treatment plants (WWTP) reached the groundwater when they drained through a fractured karst vadose zone (WWTP-K) and a porous vadose zone (WWTP-P). Forty-five samples of sewage water (SW), treated water (TW), and monitoring well (MW), collected from WWTP-P (24) and WWTP-K (21), were analyzed for a range of microbiological and chemical properties. The E. coli and Salmonella counts were below the limits outlined in the Legislative Decree 152/06 in effluents from both types of WWTP. Enteric viruses were found in 37.5% and 12.5% of the SW and TW from WWTP-P, respectively. The percentages of Pepper mild mottle virus isolated were higher in TW (62.5% in WWTP-P, 85.7% in WWTP-K) than in SW and MW. The residual concentrations of contaminants of emerging concern (CEC) of each drug category were higher in the MW downstream of WWTP-K than of WWTP-P. Our results showed that the porous vadose zone was more effective at reducing the contaminant loads than the fractured karst one, especially the CEC, in the effluent. The legislation should include other parameters to minimize the risks from treated effluent that is discharged to soil.
RESUMO
Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using one pre-defined method and one locally (i.e. in-house) developed method. The data generated represents a valuable resource (i.e. benchmark) for future developments of algorithms and workflows for NTA experiments.
Assuntos
Benchmarking , Água Potável/análise , Espectrometria de Massas , Algoritmos , Laboratórios , Fluxo de TrabalhoRESUMO
This study investigated the environmental contamination of groundwater as a consequence of the discharge of treated wastewater into the soil. The investigation focused on a wastewater treatment plant located in an area fractured by karst in the Salento peninsula (Apulia, Italy). Water samples were collected at four sites (raw wastewater, treated wastewater, infiltration trench, and monitoring well), monthly from May to December 2019 (with the exception of August), and were tested for (1) panel of bacteria; (2) enteric viruses; and (3) chemical substances. A gradual reduction in the concentration of bacteria, viruses and contaminants of emerging concern was observed across the profile of soil fissured by karst. All monitored bacteria were absent from the monitoring well, except for Pseudomonas aeruginosa. Pepper mild mottle virus and adenovirus were detected at all sampling sites. Personal care products and X-ray contrast media showed the greatest decrease in concentration from infiltration trench to the monitoring well, while the highest residual concentrations in the monitoring well were found for anticonvulsants (78.5%), antimicrobials (41.3%), and antipsychotic drugs (38.6%). Our results show that parameters provided by current law may not always be sufficient to evaluate the sanitary risk relating to the discharge of treated wastewater to the soil.
RESUMO
Efforts are made to perform an early and accurate detection of hepatocellular carcinoma (HCC) by simultaneous exploiting multiple clinically non-invasive imaging modalities. Original nanostructures derived from the combination of different inorganic domains can be used as efficient contrast agents in multimodal imaging. Superparamagnetic iron oxide nanoparticles (SPIONs) and Au nanoparticles (NPs) possess well-established contrasting features in magnetic resonance imaging (MRI) and X-ray computed tomography (CT), respectively. HCC can be targeted by using specific carbohydrates able to recognize asialoglycoprotein receptor 1 (ASGPR1) overexpressed in hepatocytes. Here, two different thiocarbohydrate ligands were purposely designed and alternatively conjugated to the surface of Au-speckled silica-coated SPIONs NPs, to achieve two original nanostructures that could be potentially used for dual mode targeted imaging of HCC. The results indicated that the two thiocarbohydrate decorated nanostructures possess convenient plasmonic/superparamagnetic properties, well-controlled size and morphology and good selectivity for targeting ASGPR1 receptor.
Assuntos
Receptor de Asialoglicoproteína/metabolismo , Carboidratos/química , Carcinoma Hepatocelular/diagnóstico por imagem , Ouro , Nanopartículas Magnéticas de Óxido de Ferro/química , Nanopartículas Metálicas/química , Dióxido de Silício , Compostos de Sulfidrila/química , Humanos , Neoplasias Hepáticas/diagnóstico por imagem , Imageamento por Ressonância MagnéticaRESUMO
Sediment toxicity plays a fundamental role in the health of inland fish communities; however, the assessment of the hazard potential of contaminated sediments is not a common objective in environmental diagnostics or remediation. This study examined the potential of transcriptional endpoints investigated in zebrafish (Danio rerio) exposed to riverbed sediments in ecotoxicity testing. Embryo-larval 10-day tests were conducted on sediment samples collected from five sites (one upstream and four downstream of the city of Milan) along a polluted tributary of the Po River, the Lambro River. Sediment chemistry showed a progressive downstream deterioration in river quality, so that the final sampling site showed up to eight times higher concentrations of, for example, triclosan, galaxolide, PAH, PCB, BPA, Ni, and Pb, compared with the uppermost site. The embryo/larval tests showed widespread toxicity although the middle river sections evidenced worse effects, as evidenced by delayed embryo development, hatching rate, larval survival, and growth. At the mRNA transcript level, the genes encoding biotransformation enzymes (cyp1a, gst, ugt) showed increasing upregulations after exposure to sediment from further downstream sites. The genes involved in antioxidant responses (sod, gpx) suggested that more critical conditions may be present at downstream sites, but even upstream of Milan there seemed to be some level of oxidative stress. Indirect evidences of potential apoptotic activity (bcl2/bax < 1) in turn suggested the possibility of genotoxic effects. The genes encoding for estrogen receptors (erα, erß1, erß2) showed exposure to (xeno)estrogens with a progressive increase after exposure to sediments from downstream sites, paralleled by a corresponding downregulation of the ar gene, likely related to antiandrogenic compounds. Multiple levels of thyroid disruption were also evident particularly in downstream zebrafish, as for thyroid growth (nkx2.1), hormone synthesis and transport (tg, ttr, d2), and signal transduction (trα, trß). The inhibition of the igf2 gene reasonably reflected larval growth inhibitions. Although none of the sediment chemicals could singly explain fish responses, principal component analysis suggested a good correlation between gene transcripts and the overall trend of contamination. Thus, the combined impacts from known and unknown covarying chemicals were proposed as the most probable explanation of fish responses. In summary, transcriptional endpoints applied to zebrafish embryo/larval test can provide sensitive, comprehensive, and timeliness information which may greatly enable the assessment of the hazard potential of sediments to fish, complementing morphological endpoints and being potentially predictive of longer studies.
Assuntos
Poluentes Químicos da Água/análise , Peixe-Zebra , Animais , Embrião não Mamífero , Sistema Endócrino , Sedimentos Geológicos , Larva , RiosRESUMO
Marine sediments may represent a sink of persistent organic pollutants including polychlorinated biphenyls (PCBs), toxic compounds prone to reductive or oxidative biodegradation pathways depending on the degree of chlorination and the positions of the chlorine atoms on the biphenyl rings. Superficial marine sediments can be subjected to episodic sediment resuspension by boat traffic and wind action causing the exposure of the underlying anaerobic layer to oxygen. Under these dynamic conditions, a deeper knowledge of the adaptation capability of the autochthonous microbial communities towards severe changes of the reaction environment is required. Insights into the metabolic potential of sediment community members may contribute greatly to the definition of efficient and reliable in situ bioremediation strategies. In this study, an anaerobic PCB-dechlorinating microbial consortium, developed from the chronically polluted marine sediment of Mar Piccolo (Taranto, Italy), was used to evaluate the response of the sediment microbiome to the imposition of aerobic conditions after prolonged anaerobic incubation. Compared to the anaerobic control, a dramatic change in microbiome composition, with a marked increase of Alphaproteobacteria of up to 39.2 % of total operational taxonomic units (OTUs) was revealed by high-throughput 16S rRNA gene sequencing. Accordingly, a decrement of low chlorinated PCBs (up to 58.3⯱â¯7.5 % for PCB 18) and the concomitant appearance of genes coding for PCB-degrading biphenyl dioxygenase (bph) were observed at the end of the aerobic incubation, suggesting the occurrence of oxidative PCB biodegradation processes.
Assuntos
Alphaproteobacteria/metabolismo , Oxigênio/metabolismo , Bifenilos Policlorados/metabolismo , Sedimentos Geológicos/microbiologia , Estresse Oxidativo , Microbiologia do SoloRESUMO
Low content of micropollutants in sewage sludge, essential to allow its safe re-use in agriculture, requires effective removals during the digestion phase. To this purpose, we investigated the performance of the anaerobic-aerobic sequential digestion process applied to real waste sludge in the removal of several classes of standard pollutants, i.e. extractable organic halogens (EOXs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), di(2-ethylhexyl)phthalate and alkylphenolethoxylates. In addition, emerging pollutants were also investigated based on their widespread occurrence and on their physicochemical characteristics and eco-toxicological relevance: quaternary ammonium compounds, a number of pharmaceuticals and selected biocides. The anaerobic step was conducted at mesophilic conditions, while two operating temperatures were tested for the post-aerobic treatment, i.e. 20 and 37⯰C, respectively. Results showed that the post-aerobic digestion step enhanced the removal of all investigated standard and emerging micropollutants, even in presence of high accumulation in the anaerobic digestate (occurred for some PAHs and PCB congeners). Increased removals (up to 30%) have been generally observed at 37⯰C aerobic temperature in comparison with tests at Tâ¯=â¯20⯰C for all investigated organic micropollutants, with the only exception of halogenated compounds (i.e. EOXs and PCBs). Low biodegradability and high bioaccumulation of the investigated pollutants were successfully faced by the sequential process, which has been demonstrated as an effective alternative solution to produce digested sludge for safe agricultural re-use.
Assuntos
Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Anaerobiose , Esgotos , Temperatura , Eliminação de Resíduos LíquidosRESUMO
The occurrence of pharmaceuticals in the environment is a topic of concern. Carbamazepine (CBZ) is a widespread antiepileptic drug and due to its physical-chemical characteristics minimal removal is achieved in conventional water treatments, and thus has been suggested as a molecular marker of wastewater contamination in surface water and groundwater. The present study reports the biotransformation of CBZ by the bacterial strain Labrys portucalensis F11. When supplied as a sole carbon source, a 95.4% biotransformation of 42.69⯵M CBZ was achieved in 30â¯days. In co-metabolism with acetate, complete biotransformation was attained at a faster rate. Following a target approach, the detection and identification of 14 intermediary metabolites was achieved through UPLC-QTOF/MS/MS. Biotransformation of CBZ by the bacterial strain is mostly based on oxidation, loss of -CHNO group and ketone formation reactions; a biotransformation pathway with two routes is proposed. The toxicity of untreated and treated CBZ solutions was assessed using Vibrio Fischeri and Lepidium sativum acute toxicity tests and Toxi-Chromo Test. The presence of CBZ and/or its degradations products in solution resulted in moderate toxic effect on Vibrio Fischeri, whereas the other organisms were not affected. To the best of our knowledge this is the first report that proposes the metabolic degradation pathway of CBZ by a single bacterial strain.
Assuntos
Alphaproteobacteria/metabolismo , Biodegradação Ambiental , Carbamazepina/metabolismo , Poluentes Químicos da Água/metabolismo , Anticonvulsivantes/metabolismoRESUMO
Urban wastewater treatment plants (WWTPs) are among the main anthropogenic sources for the release of contaminants of emerging concern (CECs) into the environment, which can result in toxic and adverse effects on aquatic organisms and consequently on humans. Unfortunately, WWTPs are not designed to remove CECs and secondary (e.g., conventional activated sludge process, CAS) and tertiary (such as filtration and disinfection) treatments are not effective in the removal of most CECs entering WWTP. Accordingly, several advanced treatment methods have been investigated for the removal of CECs from wastewater, including consolidated (namely, activated carbon (AC) adsorption, ozonation and membranes) and new (such as advanced oxidation processes (AOPs)) processes/technologies. This review paper gathers the efforts of a group of international experts, members of the NEREUS COST Action ES1403 who for three years have been constructively discussing the state of the art and the best available technologies for the advanced treatment of urban wastewater. In particular, this work critically reviews the papers available in scientific literature on consolidated (ozonation, AC and membranes) and new advanced treatment methods (mainly AOPs) to analyse: (i) their efficiency in the removal of CECs from wastewater, (ii) advantages and drawbacks, (iii) possible obstacles to the application of AOPs, (iv) technological limitations and mid to long-term perspectives for the application of heterogeneous processes, and (v) a technical and economic comparison among the different processes/technologies.
RESUMO
Diclofenac (DCF) is one of the most detected pharmaceuticals in environmental water matrices and is known to be recalcitrant to conventional wastewater treatment plants. In this study, degradation of DCF was performed in water by photolysis and photocatalysis using a new synthetized photocatalyst based on hydroxyapatite and TiO2 (HApTi). A degradation of 95% of the target compound was achieved in 24 h by a photocatalytic treatment employing the HApTi catalyst in comparison to only 60% removal by the photolytic process. The investigation of photo-transformation products was performed by means of UPLC-QTOF/MS/MS, and for 14 detected compounds in samples collected during treatment with HApTi, the chemical structure was proposed. The determination of transformation product (TP) toxicity was performed by using different assays: Daphnia magna acute toxicity test, Toxi-ChromoTest, and Lactuca sativa and Solanum lycopersicum germination inhibition test. Overall, the toxicity of the samples obtained from the photocatalytic experiment with HApTi decreased at the end of the treatment, showing the potential applicability of the catalyst for the removal of diclofenac and the detoxification of water matrices.
RESUMO
Diclofenac (DCF) is a widely used non-steroidal anti-inflammatory pharmaceutical which is detected in the environment at concentrations which can pose a threat to living organisms. In this study, biodegradation of DCF was assessed using the bacterial strain Labrys portucalensis F11. Biotransformation of 70% of DCF (1.7-34⯵M), supplied as the sole carbon source, was achieved in 30 days. Complete degradation was reached via co-metabolism with acetate, over a period of 6 days for 1.7⯵M and 25 days for 34⯵M of DCF. The detection and identification of biodegradation intermediates was performed by UPLC-QTOF/MS/MS. The chemical structure of 12 metabolites is proposed. DCF degradation by strain F11 proceeds mainly by hydroxylation reactions; the formation of benzoquinone imine species seems to be a central step in the degradation pathway. Moreover, this is the first report that identified conjugated metabolites, resulting from sulfation reactions of DCF by bacteria. Stoichiometric liberation of chlorine and no detection of metabolites at the end of the experiments are strong indications of complete degradation of DCF by strain F11. To the best of our knowledge this is the first report that points to complete degradation of DCF by a single bacterial strain isolated from the environment.
Assuntos
Alphaproteobacteria/metabolismo , Diclofenaco/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Acetatos/metabolismo , Biodegradação Ambiental , Biotransformação , Diclofenaco/metabolismo , Modelos Teóricos , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/metabolismoRESUMO
The photochemical degradation of two azo and two anthraquinonic dyes was performed using potassium peroxymonosulphate (Oxone®) activated by UV radiation. The fast decolourization of all dyes was observed within 6 min of UV irradiation, with corresponding dye decays higher than 80%. The kinetic rate constants of the dyes' decay were determined, along with the energetic efficiency of the photochemical treatment, taking into account the influence of a few anions commonly present in real wastewaters (i.e., chloride, nitrate, carbonate/bicarbonate and phosphate ions). Chloride and carbonate/bicarbonate ions enhanced dye degradation, whereas phosphate ions exerted an inhibitory effect, and nitrates did not have a predictable influence. The dye decolourization was not associated with efficient mineralization, as suggested by the lack of a significant total organic carbon (TOC) decrease, as well as by the low concentrations of a few detected low molecular weight by-products, including nitrate ions, formaldehyde and organic acids. High molecular weight by-products were also detected by mass spectrometry analysis. The investigated process may be proposed as a convenient pre-treatment to help dye degradation in wastewater during combined treatment methods.
Assuntos
Antraquinonas/análise , Compostos Azo/análise , Corantes/análise , Peróxidos/química , Raios Ultravioleta , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Antraquinonas/química , Compostos Azo/química , Corantes/química , Cinética , Oxirredução , Peróxidos/efeitos da radiação , Poluentes Químicos da Água/químicaRESUMO
Amorphous titanium hydroxide and boron-doped (B-doped) sodium titanates hydrates were synthetized and used as adsorbents for the removal of Pb2+ from water. The use of sodium borohydride (NaBH4) and titanium(IV) isopropoxide (TTIP) as precursors permits a very easy synthesis of B-doped adsorbents at 298K. The new adsorbent materials were first chemically characterized (XRD, XPS, SEM, DRIFT and elemental analysis) and then tested in Pb2+ adsorption batch experiments, in order to define kinetics and equilibrium studies. The nature of interaction between such sorbent materials and Pb2+ was also well defined: besides a pure adsorption due to hydroxyl interaction functionalities, there is also an ionic exchange between Pb2+ and sodium ions even working at pH 4.4. Langmuir model presented the best fitting with a maximum adsorption capacity up to 385mg/g. The effect of solution pH and common ions (i.e. Na+, Ca2+ and Mg2+) onto Pb2+ sorption were also investigated. Finally, recovery was positively conducted using EDTA. Very efficient adsorption (>99.9%) was verified even using tap water spiked with traces of Pb2+ (50ppb).
RESUMO
The degradation of two of the most frequently used UV-filters was investigated through microcosm studies. Marine sediments sampled from two sites in Italy (La Spezia harbour and Sarno river estuary, S1 and S2 respectively) were used to set up aerobic and anaerobic sets of reactors. The sediments were spiked with a methanol solution of 3-(4-methylbenzylidene)camphor (4-MBC) and 2-ethylhexyl 4-(dimethylamino)benzoate (EH-DPAB), at concentrations of either 25 or 50mgkg-1 each. Methanol (6.3g/L) also served as an organic amendment and growth substrate for improving microbial activity. Monitoring of the biotic and abiotic degradation of the selected contaminants over 16months revealed that 4-MBC biodegradation was very slow and incomplete, whereas over 90% of EH-DPAB was degraded both in the aerobic and the anaerobic reactors by the natural microbial communities of both sediments. Repeated spikes of EH-DPAB were followed by complete decay, characterised by first-order kinetics. The calculated kinetic rate constants under aerobic and anaerobic conditions were similar. In reactors inoculated with the S1 sediment the degradation rate constants progressively increased after each spike, up to the value of 0.039d-1. For the S2 sediment the rate constant was around 0.020d-1 throughout the duration of the experiment. Mass spectrometry analysis of sediment extracts allowed detection of potential transformation products of EH-DPAB and 4-MBC. Moreover, the natural microbial community of the sediments was studied using the CAtalyzed Reporter Deposition Fluorescence In Situ Hybridization (CARD-FISH) both in the initial sediments and after degradation under aerobic and anaerobic conditions.
RESUMO
A plant-assisted bioremediation strategy was applied in an area located in Southern Italy, close to the city of Taranto, historically contaminated by polychlorinated biphenyls (PCBs) and heavy metals. A specific poplar clone (Monviso) was selected for its ability to promote organic pollutant degradation in the rhizosphere, as demonstrated elsewhere. Chemical and microbiological analyses were performed at the time of poplar planting in selected plots at different distances from the trunk (0.25-1m) and at different soil depths (0-20 and 20-40cm), at day 420. A significant decrease in PCB congeners and a reduction in all heavy metals was observed where the poplar trees were present. No evidence of PCB and heavy metal reduction was observed in the non poplar-vegetated soil. Microbial analyses (dehydrogenase activity, cell viability, microbial abundance) of the autochthonous microbial community showed an improvement in soil quality. In particular, microbial activity generally increased in the poplar-rhizosphere and a positive effect was observed in some cases at up to 1m distance from the trunk and up to 40cm depth. The Monviso clone was effective in promoting both a general decrease in contaminant occurrence and an increase in microbial activity in the chronically polluted area a little more than one year after planting.