An Electroanalytical Solution for the Determination of Pb2+ in Progressive Hair Dyes Using the Cork-Graphite Sensor.

Lead is one of the most toxic metals for living organisms: once absorbed by soft tissues, it is capable of triggering various pathologies, subsequently bioaccumulating in the bones. In consideration of this, its detection and quantification in products for human consumption and use is of great interest, especially if the procedure can be carried out in an easy, reproducible and economical way. This work presents the results of the electroanalytical determination of lead in three different commercial products used as progressive hair dyes. Analyses were performed by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV) using a composite cork-graphite sensor in 0.5M H2SO4 solution or 0.1M acetate buffer (pH 4.5), in the presence and absence of hair dye samples. The H2SO4 solution gave better results in terms of analyte sensitivity than the acetate buffer electrolyte. In both cases, well-defined signals for lead were obtained by DPSV analyses, enabling the calibration curve and figures of merit to be determined. The limits of detection (LOD) were found to be approximately 1.06 µM and 1.26 µM in H2SO4 and acetate buffer, respectively. The DPSV standard addition method was successfully applied to quantify the lead in hair dye samples, yielding values below 0.45% in Pb. All three analyzed samples were shown to comply with the limit set by the Brazilian Health Regulatory Agency, i.e., 0.6% lead in this type of product. The comparison of the electroanalytical results with those obtained by the reference method, based on the use of inductively coupled plasma optical emission spectrometry (ICP-OES), confirmed that the electroanalytical detection approach is potentially applicable as a strategy for quality control.

A pH-neutral electrolyzed oxidizing water significantly reduces microbial contamination of fresh spinach leaves.

There are growing demands globally to use safe, efficacious and environmentally friendly sanitizers for post-harvest treatment of fresh produce to reduce or eliminate spoilage and foodborne pathogens. Here, we compared the efficacy of a pH-neutral electrolyzed oxidizing water (Ecas4 Anolyte; ECAS) with that of an approved peroxyacetic acid-based sanitizer (Ecolab Tsunami® 100) in reducing the total microbial load and inoculated Escherichia coli, Salmonella Enteritidis and Listeria innocua populations on post-harvest baby spinach leaves over 10 days. The impact of both sanitizers on the overall quality of the spinach leaves during storage was also assessed by shelf life and vitamin C content measurements. ECAS at 50 ppm and 85 ppm significantly reduced the bacterial load compared to tap water-treated or untreated (control) leaves, and at similar levels (approx. 10-fold reduction) to those achieved using 50 ppm of Ecolab Tsunami® 100. While there were no obvious deleterious effects of treatment with 50 ppm Tsunami® 100 or ECAS at 50 ppm and 85 ppm on plant leaf appearance, tap water-treated and untreated leaves showed some yellowing, bruising and sliming. Given its safety, efficacy and environmentally-friendly characteristics, ECAS could be a viable alternative to chemical-based sanitizers for post-harvest treatment of fresh produce.

Neutral electrolyzed oxidizing water is effective for pre-harvest decontamination of fresh produce.

Pre-harvest sanitization of irrigation water has potential for reducing pathogen contamination of fresh produce. We compared the sanitizing effects of irrigation water containing neutral electrolyzed oxidizing water (EOW) or sodium hypochlorite (NaClO) on pre-harvest lettuce and baby spinach leaves artificially contaminated with a mixture of Escherichia coli, Salmonella Enteritidis and Listeria innocua (~1 × 108 colony-forming units/mL each resuspended in water containing 100 mg/L dissolved organic carbon, simulating a splash-back scenario from contaminated soil/manure). The microbial load and leaf quality were assessed over 7 days, and post-harvest shelf life evaluated for 10 days. Irrigation with water containing EOW or NaClO at 50 mg/L free chlorine significantly reduced the inoculated bacterial load by ≥ 1.5 log10, whereas tap water irrigation reduced the inoculated bacterial load by an average of 0.5 log10, when compared with untreated leaves. There were no visual effects of EOW or tap water irrigation on baby spinach or lettuce leaf surfaces pre- or post-harvest, whereas there were obvious negative effects of NaClO irrigation on leaf appearance for both plants, including severe necrotic zones and yellowing/browning of leaves. Therefore, EOW could serve as a viable alternative to chemical-based sanitizers for pre-harvest disinfection of minimally processed vegetables.

Enhancements in phytoremediation technology: Environmental assessment including different options of biomass disposal and comparison with a consolidated approach.

Phytoremediation represents a solution for treating soils contaminated by heavy metals, provided that appropriate plant species are selected and the proper strategy chosen. When dealing with soil contaminated with arsenic and/or lead, which are non-essential elements for plants but also among the most toxic metals, this task is particularly difficult to achieve. In a previous contribution we showed that metals accumulation by Lupinus albus, Brassica juncea and Helianthus annuus can be improved by dosing suitable chemicals (i.e. phosphate and EDTA), leading to a quicker and cheaper intervention. This study discusses the assisted phytoremediation of a real site contaminated by several metals, presenting an environmental assessment realized by using the GaBi LCA software. The environmental sustainability of the reclamation technology was analyzed in terms of Global Warming Potential (GWP-100 years), considering different destinations for the harvested biomass, and comparing its ecological footprint with the outcomes of a conventional treatment of excavation and landfill disposal. The comparison clearly shows the great advantage of the phytoremediation, in terms of environmental impact, highlighting the importance of correctly handling the disposal of contaminated biomass produced. In fact, its incineration (aimed at reducing the volumes to be disposed of) could be more onerous than a direct landfilling, but re-qualify as a more sustainable choice if combined with energy recovery. The same applies to fast pyrolysis, which seems to be the most sustainable approach to date, at least in terms of technological maturity, although this requires technical-economic considerations on the quality and use of biofuels produced.

Removal of Mn and As from drinking water by red mud and pyrolusite.

Due to limited economic resources, which impede access to specific advanced technologies, many developing countries are still facing the challenge of reducing human exposure to heavy metals, which is primarily associated with the consumption of water contaminated through the discharge of poorly treated wastewater. In wastewater treatment technology, adsorption is sometime preferred to other approaches because of its high efficiency, easy handling, availability of different substrates and cost effectiveness. Moreover, increasing emphasis has recently been given to the use of low-cost adsorbents (generally solid wastes) for the treatment of polluted water, with a resulting double benefit for the environment. In this paper, the use of red mud and pyrolusite has been investigated for the removal of As and Mn from drinking water. Adsorption equilibrium data have been examined through the application of constant temperature models (isotherms), while batch and dynamic tests have been used to clarify the effects of pH, initial metal ion concentration and temperature on the adsorption performance, aiming at identifying the best conditions for the treatment. The combined use of the two adsorbents allows exploiting their properties synergistically, maximizing efficacy and sustainability without affecting process design and costs. In particular, 'clean' water (i.e. water with heavy metals contents below law limits) has been obtained even after the passage of a volume of solution higher than 40 bed volumes, and considering initial unrealistically high concentrations for the metals.

Efficacy evaluation of a new water sanitizer for increasing the shelf life of Southern Australian King George Whiting and Tasmanian Atlantic Salmon fillets.

The bacterial species and specific spoilage organisms associated with the Southern Australian King George Whiting (KGW) and Tasmanian Atlantic Salmon (TAS), and the efficacy of a HOCl-containing water-based sanitization product (Electro-Chemically Activated Solution, by ECAS4) in extending the shelf life of KGW and TAS fillets were evaluated. Fillets were washed with an ECAS4 solution containing either 45 ppm or 150 ppm of free chlorine and bacterial species enumerated on selective and non-selective media, followed by identification of pure isolates by 16 S rRNA gene sequencing. The dominant spoilage microbiota in KGW and TAS fillets stored at 4 ± 1 °C were Pseudomonas spp. and Shewanella spp. At either concentration, ECAS4 significantly reduced total bacterial load and specific spoilage organisms on KGW and TAS fillets (approx. 1-2 log colony-forming units) during storage and significantly extended the shelf life of the fillets by 2 and 4 days, respectively. The significant increase in shelf life and quality of fillets was corroborated by raw and cooked sensory evaluation. ECAS4 sanitization could have a significant impact on the overall food industry, translating into health and economic benefits through reduction of food spoilage bacteria and potentially, foodborne pathogens without many of the disadvantages of currently approved biocides.

Electrokinetic remediation of soils contaminated by potentially toxic metals: Dedicated analytical tools for assessing the contamination baseline in a complex scenario.

In order to assess the capabilities of a remediation technology, and to judge of its efficacy, it is necessary to evaluate the initial average contamination level of the soil, an operation that can be difficult because of the inhomogeneity of the contamination itself. The goal is even more challenging when different contaminants are present, greatly differing both in terms of nature and of concentration. By referring to an industrial site contaminated mainly by As, Cd, Cu, Pb, Sb, Tl and Zn, we present a new approach for the necessary processing of sampling data, in order to establish the pre-intervention baseline: an estimate of the average contamination has been obtained through a suitable integration of the volume underlying the distribution curve of each contaminating species. This information, otherwise not accessible by means of sampling of discrete points, is useful in evaluating the effectiveness of the remediation technology under investigation, and can also be considered for other reclamation approaches as well. Since "chemometrically acceptable" results are typically achieved by increasing the number of samples (with related analytical investments), the proposed approach can help keep low these ancillary costs, while providing results that are more reliable.

The use of ECAS in plant protection: a green and efficient antimicrobial approach that primes selected defense genes.

The use of highly polluting chemicals for plant and crop protection is one of the components of the negative environmental impact of agricultural activities. In the present paper, an environmentally friendly alternative to pesticide application has been studied, based on the so-called electrochemically activated solutions (ECAS). Experiments have been carried out, by applying ECAS having different contents of active ingredients, on tobacco plants at a laboratory scale and on apple trees at fruit garden scale. The results, accumulated during a couple of years, have shown that properly selected dilute solutions of chlorides, once activated by an electrochemical treatment, exhibit a very effective protecting action of plants, irrespective of their nature. Extension of the research has shown that the observed effect is the result of two distinct factors: the expected anti-microbial action of the electrochemically synthesized oxidants, and an unexpected priming of immune plant defenses, which is clearly due to the treatment with ECAS. Interestingly, the repetition of ECAS application triggers an even stronger activation of defense genes. No oxidative damages, due to the use of the activated solutions, could be detected.

Development of FT-NIR models for the simultaneous estimation of chlorophyll and nitrogen content in fresh apple (Malus domestica) leaves.

Agricultural practices determine the level of food production and, to great extent, the state of the global environment. During the last decades, the indiscriminate recourse to fertilizers as well as the nitrogen losses from land application have been recognized as serious issues of modern agriculture, globally contributing to nitrate pollution. The development of a reliable Near-Infra-Red Spectroscopy (NIRS)-based method, for the simultaneous monitoring of nitrogen and chlorophyll in fresh apple (Malus domestica) leaves, was investigated on a set of 133 samples, with the aim of estimating the nutritional and physiological status of trees, in real time, cheaply and non-destructively. By means of a FT (Fourier Transform)-NIR instrument, Partial Least Squares (PLS) regression models were developed, spanning a concentration range of 0.577%-0.817% for the total Kjeldahl nitrogen (TKN) content (R2 = 0.983; SEC = 0.012; SEP = 0.028), and of 1.534-2.372 mg/g for the total chlorophyll content (R2 = 0.941; SEC = 0.132; SEP = 0.162). Chlorophyll-a and chlorophyll-b contents were also evaluated (R2 = 0.913; SEC = 0.076; SEP = 0.101 and R2 = 0.899; SEC = 0.059; SEP = 0.101, respectively). All calibration models were validated by means of 47 independent samples. The NIR approach allows a rapid evaluation of the nitrogen and chlorophyll contents, and may represent a useful tool for determining nutritional and physiological status of plants, in order to allow a correction of nutrition programs during the season.

Removal of polyethylene glycols from wastewater: A comparison of different approaches.

Physicochemical methods such as adsorption on activated carbon, oxidation with either ozone or Fenton reagent, and chemical precipitation (coagulation), were assessed for the removal of polyethylene glycol (PEG) from wastewater. This contaminant is rarely investigated due to its low toxicity, although its presence limits the use of large water resources. The experimental tests showed that adsorption on activated carbon is well approximated by a Langmuir isotherm, and influenced by contact time, PEG molecular weight, pH, temperature, and initial PEG concentration. Ozonation allowed fragmenting the polymeric chains but was unable to remove completely the PEG, while about 85% of the total organic carbon (TOC) was removed by Fenton oxidation reaction by using a ratio between H2O2 and FeII close to 4. Coagulation did not produce results worthy of note, most likely because the uncharged PEG molecule does not interact with the iron hydroxide flocs. However, when performed after the Fenton oxidation (i.e., by simply raising the pH to values > 8), it allowed a further reduction of the residual TOC, up to 96% of the total, in the best case. Based on the resources used by each process studied and in consideration of the effectiveness of each of them, a semi-quantitative comparison on the sustainability of the different approaches is proposed.

Umbilical cord bilirubin level and pre-discharge hyperbilirubinemia risk.

OBJECTIVES: To assess whether arterial umbilical cord bilirubin (aUCB) level at delivery predicts predischarge neonatal hyperbilirubinemia, facilitating a safe discharge from the hospital. METHODS: Prospective analysis of hospital biochemistry records identified near term and term infants with recorded aUCB and predischarge, at 36 h of life, capillary heal bilirubin (cHB), to identify those with a cutoff of bilirubin levels >9 mg/ml, >75th percentile on the nomogram of Bhutani et al. RESULTS: Of 616 study neonates, median (IQR) aUCB and cHB levels were 1.5 mg % (IQR 0.7-2.2) and 7.7 mg % (IQR 6.6-8.9), respectively. The values resulted statistically correlated (Pearson correlation coefficient 0.26, p < .0001) and an increment of 1 mg/dl in aUCB was associated with an increment (Regression coefficient, 95% confidence interval) of mean cHB 0.49 (0.33-0.65, p < .0001). Among these, 143 (23.2%) neonates developed bilirubin levels >9 mg/ml at 36 h of life and multivariable analysis confirmed that cHB levels (OR 1.49, 95% CI 1.22-1.82; p < .0001) and vaginal delivery (OR 2.34, 95% CI 1.33-4.36; p = .005) were significantly associated with bilirubin levels >9 mg/ml. CONCLUSIONS: These data suggest that aUCB should be added to the list of major risk factors for neonatal hyperbilirubinemia.

Decontamination of aerosolised bacteria from a pig farm environment using a pH neutral electrochemically activated solution (Ecas4 anolyte).

An electrochemically activated solution (ECAS), generated by electrolysis of a dilute sodium chloride solution in a four-chamber electrolytic cell (Ecas4), was tested as a sanitising aerosol in eliminating bacteria from the environment of a weaning room vacated 24-48h earlier, at a continuous flow pig farm. An ultrasonic humidifier was used to fill the environment with a fog (droplets with diameters of 1-5 µm) containing 0.25 ppm of hypochlorous acid. The weaning room was fogged for 3 min at 30 min intervals during five hours of aerosol disinfection. An innovative sample treatment with propidium monoazide dye in conjunction with cyclonic air sampling was optimised and adapted for discerning live/dead bacteria in subsequent molecular quantification steps. Without fogging, total bacterial load ranged from 5.06 ± 0.04 to 5.75 ± 0.04 Log10 CFU/m3. After the first hour of fogging, a 78% total bacterial reduction was observed, which further increased to > 97% after the second hour, > 99.4% after the third and 99.8% after the fourth hour, finally resulting in a 99.99% reduction from the farm environment over five hours. Unlike the current formaldehyde spray disinfection protocol, which requires a long empty period because of its hazardous properties, this economically viable and environmentally friendly disinfection protocol may significantly lower downtime. Moreover, ECAS fogging can be easily adapted to a variety of applications, including the elimination of pathogens from livestock farm air environment for disease prevention, as well as decontamination after disease outbreaks.

Comparative antibacterial activities of neutral electrolyzed oxidizing water and other chlorine-based sanitizers.

There is increasing demand for safe and effective sanitizers for irrigation water disinfection to prevent transmission of foodborne pathogens to fresh produce. Here we compared the efficacy of pH-neutral electrolyzed oxidizing water (EOW), sodium hypochlorite (NaClO) and chlorine dioxide (ClO2) against single and mixed populations of E. coli, Listeria and Salmonella under a range of pH and organic matter content. EOW treatment of the mixed bacterial suspension resulted in a dose-dependent (<1 mg/L free chlorine), rapid (<2 min) and effective (4-6 Log10) reduction of the microbial load in water devoid of organic matter under the range of pH conditions tested (pH, 6.0, 7.0, 8.4 and 9.2). The efficacy of EOW containing 5 mg/L free chlorine was unaffected by increasing organic matter, and compared favourably with equivalent concentrations of NaClO and ClO2. EOW at 20 mg/L free chlorine was more effective than NaClO and ClO2 in reducing bacterial populations in the presence of high (20-100 mg/L) dissolved organic carbon, and no regrowth or metabolic activity was observed for EOW-treated bacteria at this concentration upon reculturing in rich media. Thus, EOW is as effective or more effective than other common chlorine-based sanitizers for pathogen reduction in contaminated water. EOW's other characteristics, such as neutral pH and ease of handling, indicate its suitability for fresh produce sanitation.

Electrochemical disinfection of groundwater for civil use - An example of an effective endogenous advanced oxidation process.

Lab-scale experiments using real groundwater were carried out using the CabECO® reactor system in order to evaluate its suitability for producing safe water, acceptable for civil purposes. Trials were carried out in discontinuous and in continuous mode, analyzing the influence of electrical and hydraulic process parameters on the quality of treated water. The use of highly boron-doped diamond electrodes in the reactor allowed the electrosynthesis of considerable amounts of ozone. Because of the relatively high amount of chloride in the groundwater samples, a mixture of HOCl/ClO- was also synthesized. Somewhat unexpectedly, the increase in the current density in the explored range 100-1000 A m-2 was accompanied by an increase in the faradaic yield of the electrosynthesis of oxidants, which was more pronounced for ozone than for free chlorine. As reported in literature, the main radical intermediate in the relevant reactions is OH, which can lead to different oxidation products, namely ozone and HOCl/ClO-. The electrolytic treatment also caused a decrease in the concentration of minor components, including NH4+ and Br-. Other byproducts were ClO3- and ClO4-, although their concentration levels were low. Moreover, due to alkali formation at the cathode surface, the precipitation of calcium and magnesium carbonates was also observed. In addition, the experimental investigation showed that even Pseudomonas aeruginosa and Legionella could be completely removed in the treated stream, due to the unique capacity of the reactor to synthesize biocidal agents like ozone, HOCl/ClO-, and chloramines. These effects were particularly evident during batch experiments.

Eco-friendly and facile integrated biological-cum-photo assisted electrooxidation process for degradation of textile wastewater.

The present article reports an integrated treatment method viz biodegradation followed by photo-assisted electrooxidation, as a new approach, for the abatement of textile wastewater. In the first stage of the integrated treatment scheme, the chemical oxygen demand (COD) of the real textile effluent was reduced by a biodegradation process using hydrogels of cellulose-degrading Bacillus cereus. The bio-treated effluent was then subjected to the second stage of the integrated scheme viz indirect electrooxidation (InDEO) as well as photo-assisted indirect electro oxidation (P-InDEO) process using Ti/IrO2-RuO2-TiO2 and Ti as electrodes and applying a current density of 20 mA cm(-2). The influence of cellulose in InDEO has been reported here, for the first time. UV-Visible light of 280-800 nm has been irradiated toward the anode/electrolyte interface in P-InDEO. The effectiveness of this combined treatment process in textile effluent degradation has been probed by chemical oxygen demand (COD) measurements and (1)H - nuclear magnetic resonance spectroscopy (NMR). The obtained results indicate that the biological treatment allows obtaining a 93% of cellulose degradation and 47% of COD removal, increasing the efficiency of the subsequent InDEO by a 33%. In silico molecular docking analysis ascertained that cellulose fibers affect the InDEO process by interacting with the dyes that are responsible of the COD. On the other hand, P-InDEO resulted in both 95% of decolorization and 68% of COD removal, as a result of radical mediators. Free radicals generated during P-InDEO were characterized as oxychloride (OCl) by electron paramagnetic resonance spectroscopy (EPR). This form of coupled approach is especially suggested for the treatment of textile wastewater containing cellulose.

An integrated (electro- and bio-oxidation) approach for remediation of industrial wastewater containing azo-dyes: Understanding the degradation mechanism and toxicity assessment.

A hybrid approach for the remediation of recalcitrant dye wastewater is proposed. The chlorine-mediated electrochemical oxidation of real textile effluents and synthetic samples (using Ti/IrO2-RuO2-TiO2 anodes), lead to discoloration by 92% and 89%, respectively, in 100min, without significant mineralization. The remediation was obtained through biodegradation, after removing the residual bio-toxic active chlorine species via sunlight exposition. Results show that the electrochemical discoloration enhances the effluent biodegradability with about 90% COD removal employing acclimatized naphthalene-degrading bacterial consortia, within 144h. Based on results obtained through FT-IR and GC-MS, it is likely that azo group stripping and oxidative cleavage of dyes occur due to the nucleophilic attack of active chlorine species during electro-oxidation. This leads to generation of aromatic intermediates which are further desulfonated, deaminated or oxidized only at their functional groups. These aromatic intermediates were mineralized into simpler organic acids and aldehydes by bacterial consortia. Phyto-toxicity trials on Vigna radiata confirmed the toxic nature of the untreated dye solutions. An increase in root and shoot development was observed with the electrochemically treated solutions, the same was higher in case of bio-treated solutions. Overall, obtained results confirm the capability of the proposed hybrid oxidation scheme for the remediation of textile wastewater.

Heterogeneous electron-transfer rate constants for fe(h(2)o)(6)(3+/2+) at metal oxide electrodes.

The title redox couple, in noncoordinating perchlorate medium, has been used to probe the electrochemical behavior of different IrO2-based electrodes; pure oxide electrodes, as well as IrO2-SnO2 mixtures, have been investigated. The obtained results show that the electrode material strongly affects the electrochemical response. A tentative explanation, based on the different point of zero charge of the considered oxides, is presented.

A Modern Approach to Disinfection, as Old as the Evolution of Vertebrates.

The immune system of vertebrates "naturally" produces hypochlorous acid (HOCl) to fight against bacteria and pathogens. A patented electrochemical technology mirrors the above defense system, allowing the synthesis of HOCl solutions through the electrolysis of water enriched in salts, at the level of a few grams per liter. The system allows for the careful control of the pH of produced solutions, with consequent optimization of their activity. Once the HOCl is introduced into the water system; it is able to remove the biofilm from pipe network; significantly decreasing the level of Legionella colonization; within 8-10 weeks from the beginning of the disinfection approach. The technology has been applied in a variety of healthcare facilities, both in Italy and in neighboring European countries. In the present paper, two successful case studies are briefly presented: Data were obtained from experiences in two different healthcare facilities, one in Italy and the other in Germany. Destruction of biofilm was indirectly testified by an increase of total organic carbon content of water; as a consequence, and because of the dosing of the disinfecting agent, some µg/L of total halomethanes were also formed. However, both compositional features were only observed during the initial stages of the disinfection treatment.