Microbial Sensing and Removal of Heavy Metals: Bioelectrochemical Detection and Removal of Chromium(VI) and Cadmium(II).

The presence of inorganic pollutants such as Cadmium(II) and Chromium(VI) could destroy our environment and ecosystem. To overcome this problem, much attention was directed to microbial technology, whereas some microorganisms could resist the toxic effects and decrease pollutants concentration while the microbial viability is sustained. Therefore, we built up a complementary strategy to study the biofilm formation of isolated strains under the stress of heavy metals. As target resistive organisms, Rhizobium-MAP7 and Rhodotorula ALT72 were identified. However, Pontoea agglumerans strains were exploited as the susceptible organism to the heavy metal exposure. Among the methods of sensing and analysis, bioelectrochemical measurements showed the most effective tools to study the susceptibility and resistivity to the heavy metals. The tested Rhizobium strain showed higher ability of removal of heavy metals and more resistive to metals ions since its cell viability was not strongly inhibited by the toxic metal ions over various concentrations. On the other hand, electrochemically active biofilm exhibited higher bioelectrochemical signals in presence of heavy metals ions. So by using the two strains, especially Rhizobium-MAP7, the detection and removal of heavy metals Cr(VI) and Cd(II) is highly supported and recommended.

Metabolite profiling and evaluation of CYP450 interaction potential of 'Trimada'- an Ayurvedic formulation.

ETHNOPHARMACOLOGICAL RELEVANCE: Trimada is well-known polyherbal Ayurvedic formulation used in Indian Traditional medicine since ancient times. It consisted of three inebriant herbs including "Chitraka" (Plumbago zeylanica Linn. Family- Plumabaginaceae), "Musta" (Cyperus rotundus Linn. Family- Cyperaceae) and Vidanga (Embelia ribes Burm. F. Family- Myrsinaceae) in equal ratios as mentioned in Ayurveda. Trimada is traditionally used to increase the functioning of the digestive system and metabolism. Along with these, it also assists in the reduction of cholesterol as well as reduces stomach aches and chest pain. AIM OF THE STUDY: This study is aimed to identify the metabolites present in this polyherbal formulation. Further, the cytotoxicity and interaction potential of the formulation and individual herbs with Cytochrome P450 isozymes (CYP3A4, 2D6, 2C9, 1A2) was evaluated by MTT assay and CYP450 enzyme inhibition. The concentration of heavy metals was also determined. MATERIAL AND METHODS: Ultra-performance liquid chromatography-quadrupole/time-of-flight mass spectrometry (UPLC-QTOF-MS) analysis was performed to detect and identify the phytoconstituents in the formulation. Cytotoxicity of the formulation was evaluated by MTT assay. CYP450 enzyme interaction potential of the individual herbs and the Trimada formulation was carried out through CYP-CO assay and fluorometric high throughput screening (HTS) assay for individual isozymes. The content of heavy metal in the formulation was quantified by Atomic Absorption Spectroscopy. RESULTS: Trimada formulation exhibited lower cytotoxicity to human liver carcinoma cell line (HepG2). CYP-CO assay revealed that the interaction potential of individual herbs and Trimada on the liver microsomes was found to be lesser than the standard inhibitor ketoconazole. Individual herbs and Trimada formulation displayed higher IC50 values than the respective standard inhibitors in the fluorimetric assay. UPLC-QTOF-MS analysis showed the presence of a number of active phytoconstituents including sesquiterpenes, phenolic acids, benzoquinones, triterpenes and flavonoids. The heavy metal concentration in the traditional medicinal herbal formulation was found within the approved limit. CONCLUSIONS: This study suggested that the individual herbs and Trimada formulation exhibited low cytotoxicity and contributes insignificant interaction with CYP450 isozymes. So, the formulation is considered to be safe for its therapeutic management without any potential drug interaction involving CYP 450 isozymes.

Aquatic Mosses as Adaptable Bio-Filters for Heavy Metal Removal from Contaminated Water.

Heavy metals (HMs) are released into the environment by many human activities and persist in water even after remediation. The efficient filtration of solubilized HMs is extremely difficult. Phytoremediation appears a convenient tool to remove HMs from polluted water, but it is limited by the choice of plants able to adapt to filtration of polluted water in terms of space and physiological needs. Biomasses are often preferred. Aquatic moss biomasses, thanks to gametophyte characteristics, can act as live filtering material. The potential for phytoremediation of Hypnales aquatic mosses has been poorly investigated compared to aquatic macrophytes. Their potential is usually indicated as a tool for bioindication and environmental monitoring more than for pollutant removal. When phytoremediation has been considered, insufficient attention has been paid to the adaptability of biomasses to different needs. In this study the heavy metal uptake of moss Taxiphyllum barbieri grown in two different light conditions, was tested with high concentrations of elements such as Pb, Cd, Zn, Cu, As, and Cr. This moss produces dense mats with few culture needs. The experimental design confirmed the capacity of the moss to accumulate HMs accordingly to their physiology and then demonstrated that a significant proportion of HMs was accumulated within a few hours. In addition to the biosorption effect, an evident contribution of the active simplistic mass can be evidenced. These reports of HM accumulation within short time intervals, show how this moss is particularly suitable as an adaptable bio-filter, representing a new opportunity for water eco-sustainable remediation.

The Hazardous Level of Heavy Metals in Different Medicinal Plants and Their Decoctions in Water: A Public Health Problem in Brazil.

The determination of Cd, Co, Cr, Cu, Fe, Na, Zn, and Pb by inductively coupled plasma-optical emission spectrometry (ICP OES) was performed on dry matter and decoctions of the medicinal plants Cordia salicifolia, Chiococca alba (L.) Hitchc., and Echites peltata used as an appetite suppressant and diuretic in Brazil. The accuracy of the measurements was analyzed by the spike recovery test. Results showed that the concentration of these seven metals (Cd, Co, Cr, Cu, Fe, Na, and Zn) in dry plant samples is below the oral concentration of elemental impurities established by the United States Pharmacopoeia Convention (USP). However, there are no concentration limits for Fe, Na, and Zn established by the USP in drug substances and excipients. Levels higher than the recommended value by the USP were observed for Pb and the lowest for Cd, Co, Cr, and Cu, both in dried plant samples and their decoctions. In the decoctions prepared from these plants were found elements such as Cd, Co, Cr, Cu, Fe, Na, Zn, and Pb. In the decoction prepared from 40 g C. salicifolia leaves and 40 g C. alba wood, the content of Cd is above the oral daily exposure value set by the USP. Hazard index (HI) for decoctions prepared from these plants exceeded the threshold (1). Given the uncertainties associated with the estimates of toxicity values and exposure factors, futures researches should address the possible toxicity in humans. Uncontrolled selling and long-term ingestion of medicinal plants can cause toxicity and interfere with the effect of drugs. Limited knowledge on the interaction potential of medicinal plants poses a challenge and public health problem in Brazil and other countries.

Magnetite nanoparticle embedded Pectin-graft-poly(N-hydroxyethylacrylamide) hydrogel: Evaluation as adsorbent for dyes and heavy metal ions from waste water.

A pectin (Pec) based gel has been made by grafting N-hydroxyethylacrylamide (HEAA) on pectin using potassium peroxodisulphate as initiator and N,N-methylenebisacrylamide as crosslinker under microwave irradiation. The magnetite (Fe3O4) nanoparticles were incorporated within this gel via in situ diffusion of Fe2+ and Fe3+ followed by reaction with ammonia solution. The synthesized gel, pectin-graft-poly(N-hydroxyethylacrylamide) (Pec-g-PHEAA); and the magnetite containing composite (Pec-g-PHEAA/Fe3O4) were characterized by FTIR, TGA, XRD, BET and SEM techniques. The magnetic property measurement indicated ferromagnetic nature of the nanocomposite. The Pec-g-PHEAA and Pec-g-PHEAA/Fe3O4 systems were evaluated for removal of dye and metal ions from aqueous solution using Rhodamine 6G (R6G), a cationic dye; Cu(II) and Hg(II) ions. Both adsorbents showed significant adsorption capacity towards these species, with greater adsorption capacity in case of Pec-g-PHEAA/Fe3O4. Adsorption process is observed to follow both Langmuir and Freundlich isotherm models for R6G dye and Freundlich isotherm model for Cu(II) and Hg(II) ions. The adsorption was found to be a pseudo first order process for R6G and pseudo second order process for Cu(II) and Hg(II) ions. The positive values of ∆H0 and the negative values of ∆G0 indicated the adsorption process to be endothermic and spontaneous.

Bacterial and heavy metal contamination in selected commonly sold herbal medicine in Blantyre, Malawi.

Background: There has been an increase in use of herbal medicine worldwide. It is either used as a stand-alone or complementary therapy to conventional medicine due to past good experience, poverty and family traditions. In Malawi, there are no regulations governing the supply, acquisition, marketing and quality enforcement of herbal medicine. This compromises its safety thereby exposing consumers to avoidable bacteria and heavy metals leading to various adverse health effects. Methods: Cross-sectional laboratory experiments were conducted to determine bacterial and heavy metal contamination of herbal medicine commonly sold in Blantyre, Malawi. A total of 47 samples which were in three formulations namely liquid, powder and tablet were used in the experiments. 29 samples were used for bacterial limit tests and 18 samples were used for heavy metal analysis. Bacterial contamination was determined by streak plate method and biochemical tests while heavy metals were determined by atomic absorption spectroscopy. Descriptive statistics and t-tests were calculated using Microsoft excel and SPSS software programs. Results: Twenty out of the 29 samples (68.9%) were contaminated with Bacillus, coagulase negative Staphylococcus, Klebsiella, Enterobacter, Citrobacter and other-Coliform bacterial species. Most isolated microorganism was Citrobacter spp. (30%), followed by Bacillus spp. (25%). Out of 20 contaminated samples, 75% were contaminated with coliforms. From these 75% which were contaminated with coliforms, 93.3% of them exceeded WHO regulatory limit (103 CFU/g for enterobacteria). Although liquid samples had the highest level of bacterial contaminants, the count was not statistically different from other formulations (P = 0.058). For heavy metals, lead and cadmium were detected and 67% of the samples had lead levels exceeding regulatory limits. Conclusion: Levels of bacterial and lead contamination in herbal medicine from Blantyre markets are far above acceptable limits set by WHO and Canadian guidelines. The use of these herbal medicines is a major risk to the health of consumers.

Urea/ZnCl2 in situ hydrothermal carbonization of Camellia sinensis waste to prepare N-doped biochar for heavy metal removal.

Environmental benefits of biochar require a simple and effective method for preparation of functional N-doped biochar. In this study, urea/ZnCl2 was developed to prepare N-doped biochar via in situ hydrothermal carbonization (HTC) of Camellia sinensis waste at 120-280 °C for 2 h under 1.0-9.8 MPa. Physicochemical and structural properties of the N-doped biochar were investigated by Raman spectra, elemental analysis, BET surface area, SEM, TEM, XRD, and XPS. The results showed that the N content in biochar could reach up to 7.79% at 280 °C. Surface chemistry suggested that pyridinic N, pyrollic N, and graphitic N were the major N species on the biochar. Moreover, the N-doped biochar was successfully employed to remove metal ions Cu2+, Pb2+, Zn2+, and Cr6+. Adsorption data fit closely to the pseudo-second-order kinetic equation and the Langmuir adsorption isotherm model for all metal ions.

Antioxidant Potential, Phytochemicals Composition, and Metal Contents of Datura alba.

This study investigated the phytochemical characteristics and antioxidant activity in leaves, roots, stem, flower, and seed parts of Datura alba (D. alba). The study also assessed the heavy metal (Cr, Mn, Zn, and Cu) accumulation in each part of the plant. Among the phytochemicals, alkaloids were found only in leaves while tannins, flavonoids, and phenols were present in all parts of the plant. For antioxidant activity, free radical scavenging assay for 2,2-diphenyl-1-picrylhydrazyl (DPPH) was performed using ascorbic acid as the standard. Higher activity was shown by stem extract in methanol and leaf extract in n-hexane, ethyl acetate, and chloroform. Furthermore, all the target heavy metals were detected in all plant sections with the highest concentration of Zn in leaves and Cu in stem, root, flower, and seed. Due to stronger antioxidant potential and phytochemical composition, D. alba could prove as valuable prospect in pharmaceutical formulations by taking part in the antioxidant defense system against generation of free radicals.

One-step synthesis of versatile magnetic nanoparticles for efficiently removing emulsified oil droplets and cationic and anionic heavy metal ions from the aqueous environment.

Versatile polyethyleneimine (PEI)-coated Fe3O4 magnetic nanoparticles (MNPs) have been synthesized by a one-step solvothermal method. The morphologies, structures, and properties of MNPs prepared for different reaction times have been characterized through various techniques. The synthesized MNPs were then used to separate emulsified oil and cationic and anionic heavy metal ions from the aqueous environment; moreover, the effects of the temperature, pH, and ionic strength of aqueous media, the solvothermal reaction time, and the number of reuse cycles on the removal efficiency have been investigated in detail. The results showed that pseudo-second-order kinetics and the Langmuir isotherm well described the adsorption processes of Cu(II) and Cr(VI). The Langmuir model yielded maximum adsorption capacities of 66.6 mg g-1 for Cu(II) and 54.5 mg g-1 for Cr(VI) at pH 5.0 and 25 °C. The synthetic MNPs could also efficiently separate diesel oil or olive oil droplets stabilized by sodium dodecyl sulfate from aqueous media. Moreover, these MNPs could be recycled five times without showing significant loss in separation efficiency. Notably, the synthesized PEI-coated MNPs could simultaneously separate emulsified oil and cationic and anionic heavy metal ions from multicomponent wastewater. Such versatile PEI-coated MNPs displayed good affinity towards emulsified oil and cationic and anionic heavy metal ions, showing great potential for practical applications in the treatment of complicated industrial wastewater matrices. Graphical abstract Simultaneous separation of emulsified oil and cationic and anionic heavy metal ions from aqueous media by using polyethyleneimine-coated Fe3O4 magnetic nanoparticles.

Improved waste-sourced biocomposite for simultaneous removal of crude oil and heavy metals from synthetic and real oilfield-produced water.

Oil- and gas-produced water (PW) which contains various pollutants is an enormous threat to the environment. In this study, a novel low-cost bio-adsorbent was prepared from shrimp shell and acid-activated montmorillonite. The results of FT-IR spectroscopy, energy dispersive X-ray (EDX) analysis, and SEM-EDX technique indicated that the chitosan-activated montmorillonite (CTS-A-MMT) was prepared successfully. The synthesized CTS-A-MMT was applied to remove simultaneously five cationic and anionic metal species and crude oil from synthetic and real oilfield PW. The adsorption data indicated that crude oil and all studied metals (except As) were adsorbed to CTS-A-MMT in a monolayer model (best fitted by Langmuir model), while As adsorption fits well with Freundlich model. Kinetic models' evaluation demonstrated that the adsorption kinetics of metals on CTS-A-MMT are initially controlled by the chemical reaction (film diffusion) followed by intra-particle diffusion. Application of the prepared CTS-A-MMT in real oilfield PW indicated removal efficiency of 65 to 93% for metals and 87% for crude oil in simultaneous removal experiments. Presence of additional ions in PW decreased the removal of studied metals and crude oil considerably; however, the concentration of the investigated pollutants in treated PW is less than the ocean discharge criteria. It is concluded that the prepared CTS-A-MMT composite is a low-cost and effective adsorbent for treating wastewater contaminated with crude oil and heavy metals (i.e., PW).

Removal of heavy metals from aluminum anodic oxidation wastewaters by membrane filtration.

Aluminum manufacturing has been reported as one of the largest industries and wastewater produced from the aluminum industry may cause significant environmental problems due to variable pH, high heavy metal concentration, conductivity, and organic load. The management of this wastewater with a high pollution load is of great importance for practitioners in the aluminum sector. There are hardly any studies available on membrane treatment of wastewater originated from anodic oxidation. The aim of this study is to evaluate the best treatment and reuse alternative for aluminum industry wastewater using membrane filtration. Additionally, the performance of chemical precipitation, which is the existing treatment used in the aluminum facility, was also compared with membrane filtration. Wastewater originated from anodic oxidation coating process of an aluminum profile manufacturing facility in Kayseri (Turkey) was used in the experiments. The characterization of raw wastewater was in very low pH (e.g., 3) with high aluminum concentration and conductivity values. Membrane experiments were carried out with ultrafiltration (PTUF), nanofiltration (NF270), and reverse osmosis (SW30) membranes with MWCO 5000, 200-400, and 100 Da, respectively. For the chemical precipitation experiments, FeCl3 and FeSO4 chemicals presented lower removal performances for aluminum and chromium, which were below 35% at ambient wastewater pH ~ 3. The membrane filtration experimental results show that, both NF and RO membranes tested could effectively remove aluminum, total chromium and nickel (>90%) from the aluminum production wastewater. The RO (SW30) membrane showed a slightly higher performance at 20 bar operating pressure in terms of conductivity removal values (90%) than the NF 270 membrane (87%). Although similar removal performances were observed for heavy metals and conductivity by NF270 and SW30, significantly higher fluxes were obtained in NF270 membrane filtration at any pressure that there were more than three times the flux values in SW30 membrane filtration. Due to the lower heavy metal (<65%) and conductivity (<30%) removal performances of UF membrane, it could be evaluated as pretreatment followed by NF filtration to protect and extend NF membrane life. The water treated by both NF and RO could be recycled back into the process to be reused with economic and environmental benefits.

Biosurfactant-assisted phytoremediation of multi-contaminated industrial soil using sunflower (Helianthus annuus L.).

This study evaluated the use of commercial rhamnolipid biosurfactant supplementation in the phytoremediation of a soil via sunflower (Helianthus annuus L.) cultivation. The soil, obtained from an industrial area, was co-contaminated with heavy metals and petroleum hydrocarbons. The remediation tests were monitored for 90 days. The best results for removal of contaminants were obtained from the tests in which the sunflower plants were cultivated in soil with 4 mg kg-1 of the rhamnolipid. Under these conditions, reductions of 58% and 48% were obtained in the total petroleum hydrocarbon (TPH) and polycyclic aromatic hydrocarbon (PAH) concentrations, respectively; reductions in the concentrations of the following metals were also achieved: Ni (41%), Cr (30%), Pb (29%), and Zn (20%). The PCR-DGGE analysis of soil samples collected before and after the treatments verified that the plant cultivation and biosurfactants supplementation had little effect on the structure of the dominant bacterial community in the soil. The results indicated that sunflower cultivation with the addition of a biosurfactant is a viable and efficient technology to treat soils co-contaminated with heavy metals and petroleum hydrocarbons.

Fate of metals before and after chemical extraction of incinerated sewage sludge ash.

Chemical extraction of incinerated sewage sludge ash (ISSA) can effectively recycle P, but it may change the speciation and mobility of the remaining metals. This study investigated the changes of the leaching potential and distribution of metals in the chemically extracted ISSA. Batch extraction experiments with different extractants, including inorganic acids, organic acids, and chelating agents, were conducted on the ISSA collected from a local sewage sludge incinerator. The extraction of Zn, Cu, Pb, Ni, Cd, Ba, Cr and As from the ISSA and the corresponding changes of the mobility and speciation were examined. The results showed that the metals in ISSA were naturally stable because large portions of metals were associated with the residual fraction. The inorganic (HNO3 and H2SO4) and organic acids (citric acid and oxalic acid) significantly co-dissolved the metals through acid dissolution, but the reduction in the total concentrations did not tally the leaching potential of the residual metals. The increase in the exchangeable fraction due to destabilization by the extractants significantly enhanced the mobility and leachability of the metals in the residual ISSA. Chelating agents (EDTA and EDTMP) only extracted a small quantity of metals and had a marginal effect on the fate of the residual metals, but they significantly reduced the Fe/Mn oxide-bound fraction. In comparison, the bioaccessibility of residual metals were reduced to varying extent. Therefore, the disposal or reuse of chemically extracted ISSA should be carefully evaluated in view of possible increase in mobility of residual metals in the environment.

Heavy metal stabilization in contaminated soil by treatment with calcined cockle shell.

In several previous studies, the efficacy of various liming waste materials on the immobilization of heavy metals has been tested and it was found that soils contaminated with heavy metals can be stabilized using this technique. Since lime (CaO) has been identified as the main phase of calcined cockle shell (CCS), it was hypothesized that CCS could be used as a soil amendment to immobilize heavy metals in soil. However, to date, no studies have been conducted using CCS. In this study, the effectiveness of CCS powder on the immobilization of Cd, Pb, and Zn in mine tailing soil was evaluated. After 28 days of incubation, the treated soil samples were exposed to weathering (four cycles of freezing-thawing and four cycles of wetting-drying) for 8 days before being subjected to a leaching test. The results of this study revealed that the soil pH increased from 7.5 to 12.2 with the addition of 5% CCS. A similar soil pH was obtained when the soil was amended with 5% pure CaO. By leaching with 0.1 M HCl, extracted Cd, Pb, and Zn were reduced by up to 85, 85, and 91%, respectively. Therefore, CCS is suggested as a low-cost lime-based soil amendment for stabilizing heavy metals in abandoned mining sites.

Characterization of fly ash ceramic pellet for phosphorus removal.

Phosphorus has been recognized as a leading pollutant for surface water quality deterioration. In the Midwestern USA, subsurface drainage not only provides a pathway for excess water to leave the field but it also drains out nutrients like nitrogen (N) and phosphorus (P). Fly ash has been identified as one of the viable materials for phosphorus removal from contaminated waters. In this study, a ceramic pellet was manufactured using fly ash for P absorption. Three types of pellet with varying lime and clay proportions by weight (type 1: 10% lime + 30% clay, type 2: 20% lime + 20% clay, and type 3: 30% lime + 10% clay) were characterized and evaluated for absorption efficiency. The result showed that type 3 pellet (60% fly ash with 30% lime and 10% clay) had the highest porosity (14%) and absorption efficiency and saturated absorption capacity (1.98 mg P/g pellet) compared to type 1 and 2 pellets. The heavy metal leaching was the least (30 µg/L of chromium after 5 h) for type 3 pellet compared to other two. The microcosmic structure of pellet from scanning electron microscope showed the type 3 pellet had the better distribution of aluminum and iron oxide on the surface compared other two pellets. This result indicates that addition of lime and clay can improve P absorption capacity of fly ash while reducing the potential to reduce chromium leaching.

Photocatalytic processes assisted by artificial solar light for soil washing effluent treatment.

Contaminated soil has become a growing issue in recent years. The most common technique used to remove contaminants (such as metals) from the soil is the soil washing process. However, this process produces a final effluent containing chelating agents (i.e., ethylenediaminedisuccinic acid, also known as EDDS) and extracted metals (i.e., Cu, Fe, and Zn) at concentrations higher than discharge limits allowed by the Italian and Brazilian environmental law. Therefore, it is necessary to develop further treatments before its proper disposal or reuse. In the present study, soil washing tests were carried out through two sequential paths. Moreover, different artificial sunlight-driven photocatalytic treatments were used to remove Cu, Zn, Fe, and EDDS from soil washing effluents. Metal concentrations after the additional treatment were within the Brazilian and Italian regulatory limits for discharging in public sewers. The combined TiO2-photocatalytic processes applied were enough to decontaminate the effluents, allowing their reuse in soil washing treatment. Ecotoxicological assessment using different living organisms was carried out to assess the impact of the proposed two-step photocatalytic process on the effluent ecotoxicity. Graphical Abstract ᅟ.

Simultaneous application of chemical oxidation and extraction processes is effective at remediating soil Co-contaminated with petroleum and heavy metals.

Chemical extraction and oxidation processes to clean up heavy metals and hydrocarbon from soil have a higher remediation efficiency and take less time than other remediation processes. In batch extraction/oxidation process, 3% hydrogen peroxide (H2O2) and 0.1 M ethylenediaminetetraacetic acid (EDTA) could remove approximately 70% of the petroleum and 60% of the Cu and Pb in the soil, respectively. In particular, petroleum was effectively oxidized by H2O2 without addition of any catalysts through dissolution of Fe oxides in natural soils. Furthermore, heavy metals bound to Fe-Mn oxyhydroxides could be extracted by metal-EDTA as well as Fe-EDTA complexation due to the high affinity of EDTA for metals. However, the strong binding of Fe-EDTA inhibited the oxidation of petroleum in the extraction-oxidation sequential process because Fe was removed during the extraction process with EDTA. The oxidation-extraction sequential process did not significantly enhance the extraction of heavy metals from soil, because a small portion of heavy metals remained bound to organic matter. Overall, simultaneous application of oxidation and extraction processes resulted in highly efficient removal of both contaminants; this approach can be used to remove co-contaminants from soil in a short amount of time at a reasonable cost.

[Purification Effect of Piggery Wastewater with Chlorella pyrenoidosa by Immobilized Biofilm-Attached Culture].

Piggery wastewater treatment with microalgae is a biological recycling technology. To evaluate the purification effect, this study investigated the treatment of piggery wastewater at different dilution ratios with Chlorella pyrenoidosa by attached cultivation and lipid production of algae cells and explored the tolerance of Chlorella pyrenoidosa to the piggery wastewater, which has high ammonia nitrogen. The piggery wastewater was diluted with purified water 1-, 2-, 5-, and 10-fold in culture media. The removal efficiencies of COD, ammonia nitrogen, total nitrogen, and total phosphorus and the enrichment effect of the heavy metals copper, zinc, and iron were measured. Meanwhile, we investigated the lipid production of Chlorella pyrenoidosa in variously diluted wastewater (1-, 2-, 5-, and 10-fold). It turned out that the purification effects of COD, ammonia nitrogen, total nitrogen, and total phosphorus were best when the piggery wastewater was diluted 5-fold, and the removal efficiencies were 86.8%, 94.1%, 85.2%, and 84.3%, respectively. Correspondingly, the lipid content was as high as 32.7%, and the removal efficiencies of the heavy metals copper, zinc, and iron were 72.9%, 70.0%, and 73.0%, respectively. The biomass productivity was 4.21 g·(m2·d)-1 at the end of the experiment. This research makes an effective connection between microalgae and piggery wastewater, which is difficult to purify deeply, and provides a theoretical basis for achieving algal biofuel production and decreasing the cost of wastewater treatment.

From municipal/industrial wastewater sludge and FOG to fertilizer: A proposal for economic sustainable sludge management.

After a ban on the depositing of untreated sludge in landfills, the sludge from municipal and industrial water-treatment plants can be regarded as a problem. Waste products of the water treatment process can be a problem or an opportunity - a source for obtaining raw materials. In the European Union, raw sludge and fats, oil and grease (FOG) from municipal and industrial wastewater treatment plants (WWTP) cannot be deposited in any natural or controlled environment. For this reason, it must be processed (stabilized, dried) to be used later as a fertilizer, building material, or alternative fuel source suitable for co-incineration in high temperature furnaces (power plants or concrete plants). The processes of drying sludge, where heat and electricity are used, are energy consuming and economically unattractive. Beside energy efficiency, the main problem of sludge drying is in its variability of quality as a raw material. In addition to this, sludge can be contaminated by a number of organic and inorganic pollutants and organisms. Due to the presence or absence of pollutants, different end products can be economically interesting. For example, if the dried sludge contains coliform bacteria, viruses, helminths eggs or smaller quantities of heavy metals, it cannot be used as a fertilizer but can still be used as a fuel. The objectives of the current article is to present a batch-processing pilot device of sludge or digestate that allows the following: (1) low pressure and low temperature energy effective drying of from 10 to 40% remaining water content, (2) disinfection of pathogen (micro)organisms, (3) heavy metal reduction, (4) production of products of predetermined quality (e.g. containing different quantities of water; it can be used as a fertilizer, or if the percentage of water in the dry sludge is decreased to 10%, then the dried sludge can be used as a fuel with a calorific value similar to coal). An important feature is also the utilization of low-pressure technology to prevent odorous gasses from spreading into the environment. There are presented two new technologies: a) Sewage sludge or digestate drying in the vacuum chamber consumes approx. 1 kWh/dm3 of evaporated water and, therefore, reaches a price of 180-240 Euros/t Dry Matter (DM), and b) Heavy metals' reduction using adsorbing reaction with magnetite nanostructures can decrease the level of heavy metals in the sewage sludge or digestate up to 20% in one cycle, which can be repeated several times on the same sludge. The aim of the paper is to present a newly developed technology which can provide economic and safe use of moderate heavy metals polluted sewage sludge on agricultural lands as organic fertilizer and, therefore, returning the nutrients (nitrogen, phosphorous, potassium) back to the human food chain, instead of being incinerated or landfilled. The proposed drying technology is economically sustainable due to the low vacuum and temperature (35 °C-40 °C), that increases the efficiency of the heat pump (coefficient of performance 5-7,2) of the energy produced by the anaerobic digestion. Hence, the main emphasis is given to the development of: an efficient method for heavy metals' reduction in the sludge treatment chain by using chitosan covered magnetite nanoparticles, an efficient drying method in a vacuum with low temperature energy which can be exploited from sludge digestion to reduce organic matter, and an energy sustainable concept of sludge treatment, with the addition of fats, oil and grease (FOG) to produce enough biogas for sludge drying to produce fertilizer.

Preconcentration of Zn, Cu, and Ni Ions from Coffee Infusions via 8-Hydroxyquinoline Complexes on Graphene Prior to Energy Dispersive X-ray Fluorescence Spectrometry Determination.

A simple and effective preconcentration procedure based on dispersive micro solid-phase extraction prior to energy dispersive X-ray fluorescence spectrometric (EDXRF) determination of trace amounts of Ni, Cu, and Zn in coffee infusions was proposed. The method is based on the adsorption of 8-hydroxyquinoline metal complexes on micro amounts of graphene nanoparticles. In order to optimize adsorption process, the influence of some parameters such as pH, graphene mass, concentration of 8-hydroxyquinoline (8-HQ) and Triton X-100, sample volume, and sorption time were examined. At optimal preconcentration conditions, calibration curves were linear from 1 to 150 ng mL-1 for Ni and Cu and from 1 to 200 ng mL-1 for Zn. The recoveries of the metal ions were in the 95-98% range with the precision lower than 4.6%. The obtained detection limits were 0.08 ng mL-1 for Ni and 0.09 ng mL-1 for Cu and Zn. The proposed method was successfully applied to determination of Ni, Cu, and Zn in coffee infusions. Accuracy and repeatability of the proposed procedure were confirmed by the standard addition method and compared to the results obtained by ICP-OES technique.