Dry chlorination of spent nickel metal hydride battery waste for water leaching of battery metals and rare earth elements

An efficient leaching process was developed for nickel, cobalt, and the rare earth elements (REEs) from spent nickel metal hydride (NiMH) battery waste. The process involves dry chlorination with ammonium chloride in low temperature to produce water-soluble chlorinated compounds, followed by simple water leaching. The factors affecting the conversion and solubilization were studied, including the amount of ammonium chloride, residence time and temperature in dry chlorination, and solid to liquid ratio, time and temperature in water leaching. As a result, the dry chlorination process was found to produce ammonium and chloride containing products, depending on the temperature of the process: …

Biomethane production from maize and liquid cow manure – Effect of share of maize, post-methanation potential and digestate characteristics

Abstract This study investigates the co-digestion of liquid cow manure and maize with different share of maize in continuously stirred tank reactors (CSTRs). The objective was to determine the methane yield of reactor and the post-methanation potential of the digestate from different reactor trials. The highest specific methane yield (259 Nl CH 4 /kg volatile solids (VSs)) was obtained when the share of maize in the feedstock was 40% (VS) and the second highest specific methane yield was when the proportion of maize was 60% (VS) (234 Nl CH 4 /kg VS). The post-methanation potential of the digestate was determined in batch assays. The minimum value (maize 40%, 75 ± 1 Nl CH 4 /kg VS feed ) occ…

Particle size based recovery of phosphorus from combined peat and wood fly ash for forest fertilization

Abstract Correlations between the concentrations of P, K, and As with particle size in fly ash from power plants were examined with a viewpoint to obtain fractions suitable for forest fertilization. Fly ash samples from several CHP plants were fractionated by using four sieves and the five fractions were analyzed by ICP-OES; it was found that both P and K are concentrated in smallest size (

Preconcentration and speciation analysis of mercury : 3D printed metal scavenger-based solid-phase extraction followed by analysis with inductively coupled plasma mass spectrometry

A selective method for preconcentration and determination of methylmercury (MeHg) and inorganic mercury (iHg) in natural water samples at the ng L−1 level has been developed. The method involves adsorption of Hg species into a 3D printed metal scavenger and sequential elution with acidic thiourea solutions before ICP-MS determination. Experimental parameters affecting the preconcentration of MeHg and iHg such as the sample matrix, effect of the flow rate on adsorption, eluent composition, and elution mode have been studied in detail. The obtained method detection limits, considering the preconcentration factors of 42 and 93, were found to be 0.05 ng L−1 and 0.08 ng L−1 for MeHg and iHg, res…

Effect of additives on process stability of mesophilic anaerobic monodigestion of pig slaughterhouse waste

The effect of two additives on anaerobic monodigestion of pig slaughterhouse waste was studied in three laboratory scale continuously stirred tank reactors (CSTRs) operated for 242-284 days at 35°C. A higher organic loading rate (OLR), namely 2.25 kg volatile solids (VS)/m(3)d with a hydraulic retention time (HRT) of 30 d was feasible with an additive containing Fe, HCl and trace elements while an OLR of 1.5 kg VS/m(3)d (HRT 30 d) led to instabilities in CSTR with an additive consisting of Fe and HCl and in CSTR without additives. Methane yields of ca. 700 dm(3) CH(4)/kg VS(fed) were obtained in all reactors under stable conditions. Both additives decreased H(2)S concentration of the biogas…

Selective recovery of phosphorus as AlPO4 from silicon-free CFB-derived fly ash leachate

The prospect of phosphorus (P) recovery from siliceous fly ash was investigated. The phosphorus content in the pristine fly ash was 1.21%. Obtaining pure phosphorus products from fly ash is very challenging because of high concentration of other elements, silicon (Si) at 17.3% being the major contaminant. The fly ash was fractionated with sieve size of 125 μm to concentrate the phosphorus in the small-size fraction, which also facilitated the removal of 78% of silica (Si) in the solid phase. The fractionated fly ash was treated with 8 M HCl in order to remove 98% of Si by aging (5 h) of leachate until precipitation of Si-gel, and a phosphorus-rich solution is obtained. Iron (Fe) is also con…

Using the critical body residue approach to determine the acute toxicity of cadmium at varying levels of water hardness and dissolved organic carbon concentrations

Abstract The linkage between acute adverse effects of cadmium and internal cadmium levels were investigated for the oligochaete worm Lumbriculus variegatus in water at varying degrees of hardness and two different dissolved organic carbon (DOC) concentrations. The LC50s for the effect of cadmium on the survival of the worms greatly differed depending on water hardness and DOC. We found less variability in internal metal toxicity metrics (lethal residue; LR50s) than in external toxicity metrics (lethal concentration; LC50s): LC50s varied from 2.4 to 66.1 μmol/L, while LR50s varied only from 226 to 413 μmol/kg wet weight. The cadmium body burden appeared to be independent of exposure conditio…

Ultrasound-assisted sequential extraction method for the evaluation of mobility of toxic elements in contaminated soils

A method for the fast sequential extraction of toxic elements in contaminated soil samples using an ultrasonic water bath, followed by determination with inductively coupled plasma optical emission spectrometry (ICP-OES), was developed and compared with other methods introduced in the literature. The five-step sequential extraction (Tessier scheme) was shortened using ultrasound-assisted sequential extraction (UASE). The optimization of the five-step sequential extraction was based on the analysis of SRM 2710 using Tessiers’s method as a reference. Several extracting solutions with different sonication times and temperatures were tested in the optimization procedure. Concentrations of arsen…

Addition of thiourea and hydrochloric acid: Accurate nanogram level analysis of mercury in humic-rich natural waters by inductively coupled plasma mass spectrometry.

Abstract An analytical method was developed for the direct determination of total mercury in natural waters at low ng L−1 level by inductively coupled plasma mass spectrometry (ICP-MS). The presented method overcomes previously observed problems relating to poor spike recoveries by adding 0.12% thiourea in addition to 3% HCl to all samples and standards. The sample preparation is fast and easy to perform by the developed method since it requires only the addition of HCl and thiourea to the water samples. A very low instrument detection limit (0.4 ng L−1) was obtained without time-consuming preconcentration procedures. The accuracy and precision of the developed method were found excellent b…

Determination of mercury at picogram level in natural waters with inductively coupled plasma mass spectrometry by using 3D printed metal scavengers

The determination of ultra-trace concentrations of Hg in natural water samples via preconcentration using 3D printed metal scavenger technique followed by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The determination of Hg in certified reference material ERM-CA615 (groundwater) was performed with high accuracy and precision resulting in recovery of 100 ± 3% and RSD <2.5%, respectively. Selective laser sintering (SLS) 3D printing was used to fabricate the scavengers using a mixture of polyamide-12 powder with thiol-functionalized silica. The preconcentration procedure is based on the adsorption of Hg on the scavenger and followed by elution of the preconcentrated Hg …

Toxicity of silver nanoparticles to Lumbriculus variegatus is a function of dissolved silver and promoted by low sediment pH

Toxicity of silver nanoparticles (AgNPs) to benthic organisms is a major concern. The use of AgNPs in industry and consumer products leads to increasing release of AgNPs into the aquatic environment-sediments being the major sink. Effects of sediment pH on the toxicity of AgNPs to benthic oligochaeta Lumbriculus variegatus were studied in a 23-d toxicity test. Artificially prepared sediments (pH 5 and 7) were spiked with varying concentrations of uncoated AgNP, polyvinylpyrrolidone (PVP)-coated AgNP, and silver nitrate (AgNO3 ) as dissolved Ag reference. Number of individuals and biomass change were used as endpoints for the toxicity. The toxic effects were related to the bioaccessible conc…

Occurrence and recovery potential of rare earth elements in Finnish peat and biomass combustion fly ash

Rare earth elements (REEs) are highly important in the modern society as a result of their wide use in various fields of industry. Their high supply risk and increase in demand has led to classification as critical materials, and consequently, new resources for REEs are being prospected widely. Coal fly ash has been suggested as a possible secondary resource for REEs, but very little information is available regarding REE occurrence in biomass or peat derived fly ash. In this paper, fly ash samples from commercial power plants using peat and biomass as fuel were studied for REEs. The average concentration of REEs was 530 ppm, with up to 920 ppm in one fly ash. Five out of seven fly ashes we…

Effect of macro and micro nutrients addition during anaerobic mono-digestion of grass silage in leach-bed reactors

The effect of macro- (NH4Cl) (set I) and micro-nutrients (Fe, Ni, Co and Mo) (set II) addition on chemical oxygen demand (COD) solubilisation during anaerobic mono-digestion of grass silage was investigated in two sets of leach bed reactor experiments at 35°C. Results showed that addition of NH4Cl and micro-nutrients improved COD solubilisation by 18% (0.56 g SCOD g−1 volatile solids) and 7% (0.45 g SCOD g−1 VS), respectively than control. About 20–50% of the added micro-nutrients were bioavailable in the produced leachates, while the rest (50–80%) were adsorbed onto the grass silage. Results of biological methane potential assays showed that, specific methane yields of grass silage were im…

Uranyl ion complexes with long chain aminoalcoholbis(phenolate) [O,N,O,O′] donor ligands

Abstract The reaction between uranyl nitrate hexahydrate and phenolic ligand precursor [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-4-amino-1-butanol) · HCl], H3L1 · HCl, leads to a uranyl complex [UO2(H2L1)2] (1a) and [UO2(H2L1)2] · 2CH3CN (1b). The ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-4-amino-1-butanol)H3L2 · HCl], H3L2 · HCl, yields a uranyl complex with a formula [UO2(H2L2)2] · CH3CN (2). The ligand [(N,N-bis(2-hydroxy-3,5-dimethylbenzyl)-5-amino-1-pentanol) · HCl], H3L3 · HCl, produces a uranyl complex with a formula [UO2(H2L3)2] · 2CH3CN (3) and the ligand [(N,N-bis(2-hydroxy-5-tert-butyl-3-methylbenzyl)-5-amino-1-pentanol) · HCl], H3L4 · HCl, leads to a uranyl complex w…

Hyperspectral Imaging of Macroinvertebrates : a Pilot Study for Detecting Metal Contamination in Aquatic Ecosystems

The applicability of spectral analysis in detection of freshwater metal contamination was assessed by developing and testing a novel hyperspectral imaging (HSI) application for aquatic insect larvae (Trichoptera: Hydropsychidae). Larvae were first exposed to four different cadmium (Cd) concentrations: 0, 1, 10, and 100 μg L−1 for 96 h. Individual larvae were then preserved in ethanol, inspected with microscopy for the number of anomalies in larval gills, and imaged by hyperspectral camera operating with wavebands between 500 and 850 nm. Three additional larvae from each exposure were analyzed for tissue Cd concentration. Although the larval tissue Cd concentrations correlated positively wit…

Järjestyslukuihin perustuva eksponentiaalinen tasoitus ja volatiliteetin ennustaminen

The determination of antimony and arsenic concentrations in fly ash by hydride generation inductively coupled plasma optical emission spectrometry

Abstract Hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES) was used in the determination of As and Sb concentrations in fly ash samples. The effect of sample pre-treatment reagents and measurement parameters used for hydride generation was evaluated. Due to memory effects observed, the appropriate read delay time was adjusted to 60 s resulting in RSDs 0.6% and 2.3% for As and Sb, respectively. The most suitable volumes of pre-reduction reagents for 10 mL of sample were 4 mL of KI/ascorbic acid (5%) and 6 mL of HCl (conc.). The determination of Sb was significantly interfered by HF, but the interference could be eliminated by adding 2 mL of saturated bo…

Optimizing the H3PO4 leaching conditions of post-precipitated sewage sludge using response surface methodology

The leaching procedure of post-precipitated aluminium phosphate sludge with dilute phosphoric acid was developed. The leaching offers a route to recover both critical phosphorous from sewage sludge and the metal used in precipitation. Using phosphoric acid as leaching solution makes it possible to continue the recovery process without the need to remove chloride or sulfate anions. The optimization of the leaching was based on experimental three-level-four-variable central composite face-centered design. The four variables included were acid concentration, volume of acid, temperature and time of leaching. The leaching was conducted for dewatered and water-containing sludge (total solid conte…

Partitioning of nanoparticle-originated dissolved silver in natural and artificial sediments

Sediments are believed to be a major sink for silver nanoparticles (AgNPs) in the aquatic environment, but there is a lack of knowledge about the environmental effects and behavior of AgNPs in sediments. The release of highly toxic Ag+ through dissolution of AgNPs is one mechanism leading to toxic effects in sediments. We applied an ultrasound-assisted sequential extraction method to evaluate the dissolution of AgNPs and to study the partitioning of dissolved Ag in sediments. Silver was spiked into artificial and 2 natural sediments (Lake Höytiäinen sediment and Lake Kuorinka sediment) as silver nitrate (AgNO3), uncoated AgNPs, or polyvinylpyrrolidone-coated AgNPs (PVP-AgNPs). In addition, …

Zinc removal in anaerobic sulphate-reducing liquid substrate process

Abstract Zinc and sulphate removal from synthetic wastewater was investigated by using four laboratory parallel upflow-mode reactors (referred as R1 to R4; R1 contained carriers to retain biomass, whereas R2–R4 were operated as suspended reactors). All reactors were inoculated with anaerobically digested cow manure. R1 and R2 were first fed with glucose- and sulphate-containing feed for 48 days after which all four reactors were fed with wastewater containing 50 mg l−1 of zinc in R1–R3 and 200 mg l−1 in R4 and operated for 96 days. In all reactors, hydraulic retention time, organic loading rate, and sulphate load were 5–6 d, 0.2–0.4 kg COD m−3 d−1 and 3.3–3.8 g SO4 l−1 d−1, respectively, wh…

Alkyl-Substituted Aminobis(phosphonates) : Efficient Precipitating Agents for Rare Earth Elements, Thorium, and Uranium in Aqueous Solutions

The efficient and environmentally sustainable separation process for rare earth elements (REE), especially for adjacent lanthanoids, remains a challenge due to the chemical similarity of REEs. Tetravalent actinoids, thorium, and traces of uranium are also present in concentrates of REEs, making their separation relevant. This study reports six simple water-soluble aminobis(phosphonate) ligands, RN[CH2P(O)(OH)2]2 (1 R = CH2CH3, 2 R = (CH2)2CH3, 3 R = (CH2)3CH3, 4 R = (CH2)4CH3, 5 R = (CH2)5CH3, 6 R = CH2CH(C2H5)(CH2)3CH3) as precipitating agents for REEs, Th, and U, as well as gives insight into the coordination modes of the utilized ligands with REEs at the molecular level. Aminobis(phospho…

An ultrasound-assisted digestion method for the determination of toxic element concentrations in ash samples by inductively coupled plasma optical emission spectrometry.

Abstract A method of ultrasound-assisted digestion followed by inductively coupled plasma optical emission spectrometry (ICP-OES) used for the determination of toxic element concentrations (arsenic, barium, cobalt, copper, lead, nickel, strontium, vanadium and zinc) in ash samples was developed. All the measurements were performed in robust plasma conditions which were tested by measuring the Mg(II) 280.270 nm/Mg(I) 285.213 nm line intensity ratios. The highest line intensity ratios were observed when a nebulizer gas flow of 0.6 L min−1, auxiliary gas flow of 0.2 L min−1 and plasma power of 1400 W were used for radially viewed plasma. The analysis of SRM 1633b showed that the ultrasound-ass…

Comparison of ultrasound-assisted extraction, microwave-assisted acid leaching and reflux for the determination of arsenic, cadmium and copper in contaminated soil samples by electrothermal atomic absorption spectrometry

Extraction methods for the determination of arsenic, cadmium, and copper in contaminated soil samples by Zeeman effect electrothermal atomic absorption spectrometry have been compared. The determination of cadmium and copper in ultrasound-assisted aqua regia extracts of contaminated soil SRMs by ETAAS, using a mixture of NH4H2PO4 and Mg(NO3)2, for cadmium, and a mixture of Pd and Mg(NO3)2, for copper, as a matrix modifier, was carried out with high accuracy and precision (RSD < 5.1%). The analysis of SRM 2711 failed to obtain the certified concentrations of Cd and Cu by microwave and reflux methods, respectively. The determination of arsenic was performed successfully in low chloride concen…

Toxicity Testing of Silver Nanoparticles in Artificial and Natural Sediments Using the Benthic Organism Lumbriculus variegatus

The increased use of silver nanoparticles (AgNP) in industrial and consumer products worldwide has resulted in their release to aquatic environments. Previous studies have mainly focused on the effects of AgNP on pelagic species, whereas few studies have assessed the risks to benthic invertebrates despite the fact that the sediments act as a large potential sink for NPs. In this study, the toxicity of sediment-associated AgNP was evaluated using the standard sediment toxicity test for chemicals provided by the Organization of Economic Cooperation and Development. The freshwater benthic oligochaete worm Lumbriculus variegatus was exposed to sediment-associated AgNP in artificial and natural …

Gold Nanoparticles on 3D-Printed Filters : From Waste to Catalysts

Three-dimensionally printed solid but highly porous polyamide-12 (PA12) plate-like filters were used as selective adsorbents for capturing tetrachloroaurate from acidic solutions and leachates to prepare PA12–Au composite catalysts. The polyamide-adsorbed tetrachloroaurate can be readily reduced to gold nanoparticles by using sodium borohydride, ascorbic acid, hydrogen peroxide, UV light, or by heating. All reduction methods led to polyamide-anchored nanoparticles with an even size distribution and high dispersion. The particle sizes were somewhat dependent on the reduction method, but the average diameters were typically about 20 nm. Particle sizes were determined by using a combination of…

The determination of trace element concentrations in fly ash samples using ultrasound-assisted digestion followed with inductively coupled plasma optical emission spectrometry.

Abstract A method of ultrasound-assisted digestion followed by inductively coupled plasma optical emission spectrometry (ICP-OES) used for the determination of trace element (chromium, copper, lead, nickel, vanadium and zinc) concentrations in fly ash samples was developed. All the measurements were performed in robust plasma conditions. Ultrasound-assisted digestion procedures using digestion solutions of aqua regia and hydrofluoric acid (HF) resulted in recovery rates of over 80% for all the analyte elements. Ultrasound-assisted two-step digestion with digestion solutions of 6 mL of HNO3 (Step 1) and 3 mL of HNO3 + 3 mL of HF (Step 2) resulted in recovery rates of over 92% for all the ana…

Separation of palladium and silver from E-waste leachate : effect of nitric acid concentration on adsorption to Thiol scavenger

The development of recovery techniques for metals present in low concentrations in E-waste, such as silver and palladium, is important from the aspect of the circular economy. Adsorption of palladium and silver was studied in detail in a batch process with silica-based Thiol scavenger from nitric acid leachate of waste printed circuit boards (PCBs). High adsorption efficiencies of Pd(II) and Ag(I), >97%, were reached in nitric acid concentrations below 3 mol L−1. At higher acid concentrations, adsorption efficiency of Ag(I) decreased drastically which enables the separation of Ag(I) and Pd(II) based on nitric acid concentration in sample solution. Pd(II) and Ag(I) followed pseudo 2nd order …

Toxicity of silver nanoparticles to Lumbriculus variegatus is a function of dissolved silver and promoted by low sediment pH

Toxicity of silver nanoparticles (AgNPs) to benthic organisms is a major concern. The use of AgNPs in industry and consumer products leads to increasing release of AgNPs into the aquatic environment—sediments being the major sink. Effects of sediment pH on the toxicity of AgNPs to benthic oligochaeta Lumbriculus variegatus were studied in a 23‐d toxicity test. Artificially prepared sediments (pH 5 and 7) were spiked with varying concentrations of uncoated AgNP, polyvinylpyrrolidone (PVP)‐coated AgNP, and silver nitrate (AgNO3) as dissolved Ag reference. Number of individuals and biomass change were used as endpoints for the toxicity. The toxic effects were related to the bioaccessible conce…

Alkyl-Substituted Aminobis(phosphonates)Efficient Precipitating Agents for Rare Earth Elements, Thorium, and Uranium in Aqueous Solutions

The efficient and environmentally sustainable separation process for rare earth elements (REE), especially for adjacent lanthanoids, remains a challenge due to the chemical similarity of REEs. Tetravalent actinoids, thorium, and traces of uranium are also present in concentrates of REEs, making their separation relevant. This study reports six simple water-soluble aminobis(phosphonate) ligands, RN[CH2P(O)(OH)2]2 (1 R = CH2CH3, 2 R = (CH2)2CH3, 3 R = (CH2)3CH3, 4 R = (CH2)4CH3, 5 R = (CH2)5CH3, 6 R = CH2CH(C2H5)(CH2)3CH3) as precipitating agents for REEs, Th, and U, as well as gives insight into the coordination modes of the utilized ligands with REEs at the molecular level. Aminobis(phospho…

Optimization of operating conditions of axially and radially viewed plasmas for the determination of trace element concentrations from ultrasound-assisted digests of soil samples contaminated by lead pellets

Abstract The method of ultrasound-assisted extraction followed by inductively coupled plasma optical emission spectrometry (ICP-OES) used for the determination of trace element concentrations (arsenic, copper, lead, antimony, and zinc) in shooting range areas was optimized. Optimization was achieved not only on the basis of the analysis of appropriate standard reference materials but also on that of 31 synthetic mixtures of matrix and analyte elements (aluminum, antimony, arsenic, calcium, copper, lead, iron, manganese, silicon, and zinc), in five concentrations. All the measurements were performed in robust plasma conditions which were tested by measuring the Mg II 280.270 nm/Mg I 285.213 …

Selective recovery of gold from electronic waste using 3D-printed scavenger

Around 10% of the worldwide annual production of gold is used for manufacturing of electronic devices. According to the European Commission, waste electric and electronic equipment is the fastest growing waste stream in the European Union. This has generated the need for an effective method to recover gold from electronic waste. Here, we report a simple, effective, and highly selective nylon-12-based three-dimensional (3D)-printed scavenger objects for gold recovery directly from an aqua regia extract of a printed circuit board waste. Using the easy to handle and reusable 3D-printed meshes or columns, gold can be selectively captured both in a batch and continuous flow processes by dipping …

An uptake and elimination kinetics approach to assess the bioavailability of chromium, copper, and arsenic to earthworms (Eisenia andrei) in contaminated field soils

The aim of this study was to determine the bioavailability of metals in field soils contaminated with chromated copper arsenate (CCA) mixtures. The uptake and elimination kinetics of chromium, copper, and arsenic were assessed in the earthworm Eisenia andrei exposed to soils from a gradient of CCA wood preservative contamination near Hartola, Finland. In soils contaminated with 1480–1590 mg Cr/kg dry soil, 642–791 mg Cu/kg dry soil, and 850–2810 mg Ag/kg dry soil, uptake and elimination kinetics patterns were similar for Cr and Cu. Both metals were rapidly taken up and rapidly excreted by Eisenia andrei with equilibrium reached within 1 day. The metalloid As, however, showed very slow uptak…

Stabilisation of MSWI bottom ash with sulphide-rich anaerobic effluent.

Effluent of an anaerobic sulphate-reducing wastewater treatment process was used to stabilise bottom ash. The effect of stabilisation on the concentration and binding of Ca, P, S, Cu, Pb, Zn, As, Cr, and Mo were studied by comparing results of sequential extraction from fresh and stabilised bottom ash. The stabilisation treatment improved the retention of Ca, Cu, Pb, S, and Zn in bottom ash compared to a treatment with ion-exchanged water. In addition to retention, Cu, S, and Zn were accumulated from the anaerobic effluent in the bottom ash. Concentrations of As, Cr, and Mo remained on the same level, whereas leaching of P increased compared to control treatment with ion-exchanged water. Im…

Removal of silicon from CFB-derived fly ash leachate in the context of phosphorus recovery

High concentrations of dissolved silica in the acid leachate impose two major challenges on precipitation based recovery of phosphorus (P). Firstly, co-precipitation of colloidal silica in the acidic regimes decreases the purity and value of precipitated P-products. In addition, silica scaling on internal surfaces of equipment is also a problematic issue in industrial operations. Therefore, removal of dissolved silica prior to P-recovery process minimizes the risks of Si-contamination in P-products and Si-scaling. In the present study, silica removal was achieved by accelerated silica polymerization with higher acidity and ionic strength of mineral acid, which also assisted the leaching of …

Effects of earthworms on decomposition and metal availability in contaminated soil: Microcosm studies of populations with different exposure histories

Abstract Population-specific differences in the responses of earthworms to simultaneous exposure to Cu and Zn were studied in microcosm experiments. Two populations of Aporrectodea caliginosa tuberculata (Eisen) with different metal exposure histories were chosen for the studies. Microcosms were prepared containing either uncontaminated soil or soils with low or high combined Cu/Zn -concentrations (79/139 or 178/311 mg kg −1 dry mass of soil, respectively). Earthworms from each population were introduced to the microcosm treatments with some microcosms serving as controls without earthworms. One series of microcosms was destructively sampled after 16 weeks incubation in a climate chamber. S…

Effective Recovery Process of Copper from Waste Printed Circuit Boards Utilizing Recycling of Leachate

AbstractThis study presents an optimized leaching and electrowinning process for the recovery of copper from waste printed circuit boards including studies of chemical consumption and recirculation of leachate. Optimization of leaching was performed using response surface methodology in diluted sulfuric acid and hydrogen peroxide media. Optimum leaching conditions for copper were found by using 3.6 mol L−1 sulfuric acid, 6 vol.% hydrogen peroxide, pulp density of 75 g L−1 with 186 min leaching time at 20°C resulting in complete leaching of copper followed by over 92% recovery and purity of 99.9% in the electrowinning. Study of chemical consumption showed total decomposition of hydrogen pero…

Tolerance of whitefish (Coregonus lavaretus) early life stages to manganese sulfate is affected by the parents

European whitefish (Coregonus lavaretus) embryos and larvae were exposed to 6 different manganese sulfate (MnSO4) concentrations from fertilization to the 3-d-old larvae. The fertilization success, offspring survival, larval growth, yolk consumption, embryonic and larval Mn tissue concentrations and transcript levels of detoxification-related genes were measured in the long-term incubation. Full factorial breeding design (4 females x 2 males) enabled examining the significance of both female and male effects, and female-male interactions in conjunction with the MnSO4 exposure on the observed endpoints. The MnSO4 exposure reduced the survival of the whitefish early life stages. Also the offs…

Toxicity of Mining-Contaminated Lake Sediments to Lumbriculus variegatus

AbstractBoreal lakes with soft water and low buffering capacity are susceptible to excess ion loading resulting from metal mining. The impact of two Finish mining sites in downstream lakes was assessed with a chronic sediment toxicity test using a laboratory-reared freshwater Lumbriculus variegatus (Oligochaeta). The test organisms were exposed to mining-contaminated natural lake sediments and hypolimnion water (HLW) or artificial freshwater (AFW) as overlying water in two independent experimental setups. In both test setups, growth and reproduction of L. variegatus were lower in sediments from the lakes receiving high amount of mining effluents from the mines nearby. In the biomining site,…

Uranyl Complexes of Alkyl-Bridged Ditopic Diaminotetraphenol Ligands and Their Use as Uranyl Ion Extractors

The coordination chemistry of uranyl ions was studied using long n-alkyl chain (n = 5-8) bridged by N,N,N',N'-tetrakis(2-hydroxy-3-methyl-5-tert-butylbenzyl)diaminoalkanes (H4L1-H4L4) as ligands. All ligands formed 2:1 (U-to-L ratio) complexes with uranyl ions, but in addition 1:1 complexes could be characterized using ligands H4L2 and H4L3. The complexes were characterized by elemental analysis, spectroscopy (IR and NMR), and X-ray diffraction. The 2:1 complexes are of two types: [(UO2)2(H2Lm)(NO3)2(solvent)2] (m = 1 and 2; solvent = ethanol or propanol) or (cation)2[(UO2)2(H2Lm)(NO3)2(anion)2]·xsolvent (m = 2 and 4; cation = triethylammonium, anion = nitrate or thiocyanate, and solvent = …

Porous 3D Printed Scavenger Filters for Selective Recovery of Precious Metals from Electronic Waste

Selective laser sintering (SLS) 3D printing is used to fabricate highly macroporous ion scavenger filters for recovery of Pd and Pt from electronic waste. The scavengers are printed by using a mixture of polypropylene with 10 wt% of type‐1 anion exchange resin. Porosities and the flow‐through properties of the filters are controlled by adjusting the SLS printing parameters. The cylinder‐shaped filters are used in selective recovery of Pd and Pt from acidic leachate of electronic waste simply by passing the solution through the object. Under such conditions, the scavenger filters are able to capture Pd and Pt as anionic complexes with high efficiency from a solution containing mixture of dif…

Determination of mineral and trace element concentrations in pine needles by ICP-OES: evaluation of different sample pre-treatment methods

In the present study, the determination of mineral and trace elements (Al, B, Ca, Cu, Fe, K, Mg, Mn, Na, P and Zn) from pine needles using three sample pre-treatment methods followed by inductively coupled plasma optical emission spectrometry, was examined. Sample pre-treatment methods tested were microwave digestion, ultrasound-assisted digestion and dry ashing. The new ultrasound-assisted digestion method was optimised by the analysis of the standard reference material (SRM) 1575a (pine needles) sample. The speed of dry ashing method was significantly increased by ultrasound dissolution after ashing. All the ICP-OES measurements were performed in robust plasma conditions which were tested…

Sulphate-Reducing Laboratory-Scale High-Rate Anaerobic Reactors for Treatment of Metal- and Sulphate-Containing Mine Wastewater

Upflow anaerobic sludge blanket (UASB) reactors were used in this study to evaluate the feasibility of the sulphate-reducing, anaerobic high-rate process to treat metal- and sulphate-containing mining wastewater (MWW). Four simultaneous reactors, inoculated with different inocula (mesophilic granular sludge from two UASB reactors, one treating sugar refinery wastewater and the other board mill wastewater) and operated with different loadings, were for 95 days fed with synthetic feed consisting of glucose and sulphate. In all reactors, 23-72% of sulphate and 12-93% of COD were removed. Subsequently, two reactors were fed with diluted MWW (zinc as the main metal) for 77 days with hydraulic re…

Partitioning of nanoparticle-originated dissolved silver in natural and artificial sediments

Sediments are believed to be a major sink for silver nanoparticles (AgNPs) in the aquatic environment, but there is a lack of knowledge about the environmental effects and behavior of AgNPs in sediments. The release of highly toxic Ag+ through dissolution of AgNPs is one mechanism leading to toxic effects in sediments. We applied an ultrasound-assisted sequential extraction method to evaluate the dissolution of AgNPs and to study the partitioning of dissolved Ag in sediments. Silver was spiked into artificial and 2 natural sediments (Lake Hoytiainen sediment and Lake Kuorinka sediment) as silver nitrate (AgNO3 ), uncoated AgNPs, or polyvinylpyrrolidone-coated AgNPs (PVP-AgNPs). In addition,…

Control of matrix interferences by the multiple linear regression model in the determination of arsenic, antimony and tin in lead pellets by inductively coupled plasma atomic emission spectrometry

A multiple linear regression technique was used to evaluate the matrix interferences in the determination of hydride-forming elements in lead shotgun pellets by inductively coupled plasma atomic emission spectrometry. The determination of arsenic, antimony, and tin in SRM C2416 (Bullet Lead) by ICP-AES failed to obtain the certified concentrations at the 95% level of confidence using the t-test. However, it proved possible, by using the multiple linear regression technique, to correct the concentrations of all three elements to a statistically acceptable level. This method of correction is based on the multiple regression line obtained from the analysis of 19 synthetic mixtures of matrix el…

Weathering of gasification and grate bottom ash in anaerobic conditions

Abstract The effect of anaerobic conditions on weathering of gasification and grate bottom ash were studied in laboratory lysimeters. The two parallel lysimeters containing the same ash were run in anaerobic conditions for 322 days, after which one was aerated for 132 days. The lysimeters were watered throughout the study and the quality of leachates and changes in the binding of elements into ash were observed. The results show that organic carbon content and initial moisture of ashes are the key parameters affecting the weathering of ashes. In the grate ash the biodegradation of organic carbon produced enough CO 2 to regulate pH. In contrast the dry gasification ash, containing little org…

Preparation and characterization of sodium iron titanate ion exchanger and its application in heavy metal removal from waste waters.

Abstract The ion exchange properties of sodium iron titanates, namely, NaFeTiO4, Na2Fe2Ti6O16 and iron-doped sodium nonatitanate were investigated. Conventional solid state and sol–gel methods were used in the synthesis of the sodium iron titanates. Structural characterization of the materials was performed with powder X-ray diffraction (XRD), thermogravimetry (TG), scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) and with inductively coupled plasma optical emission spectrometry (ICP-OES). Based on TG analyses, the novel iron-doped sodium nonatitanate was proven to be a member of the layered titanate family. The different sodium iron titanates were compa…

Sodium nitrate and tungsten as matrix modifiers for the determination of arsenic in shotgun pellets by electrothermal atomic absorption spectrometry

A method for the determination of arsenic in a complicated sample matrix by Zeeman effect electrothermal atomic absorption spectrometry using tungsten and sodium nitrate as matrix modifiers was developed. The determination of arsenic in SRM C2416 (Bullet Lead) and SRM 2710 (Montana Soil) by ETAAS using a mixture of palladium and magnesium nitrate as a matrix modifier failed to obtain the certified concentrations at the 95% level of confidence using the t-test. Both tungsten and sodium nitrate as matrix modifiers stabilized arsenic so that the certified concentrations of the SRMs were determined with high accuracy and precision (RSD   0.999), with low detection and quantification limits, wer…

Effects of heavy metals on earthworms along contamination gradients in organic rich soils.

Earthworm communities and metal (bio)availability to earthworms along contamination gradients was studied in order to support chemical analyses in risk assessment of metal contaminated soils. Earthworms were sampled in three metal contaminated areas with different habitat and soil properties in Finland. Earthworm and soil samples were collected at three distances (1, 2, and 4 km) from the emission sources. Earthworms were identified as to species and analyzed for heavy metals. Total soil metal concentrations were analyzed using an ultrasound-assisted extraction method and bioavailable metal fraction was estimated by acetic acid extraction. In two of the three areas studied, heavy metal conc…

Condition and Sperm Characteristics of Perch Perca fluviatilis inhabiting Boreal Lakes Receiving Metal Mining Effluents.

AbstractOne of the world’s largest, but low-grade, sulfide nickel deposits in northeastern Finland has been exploited by a bioheapleaching technology since 2008. Bioheapleaching is a relatively new, cost-effective technology, but humid climate, e.g., in boreal temperate environments, causes challenges to the management of the water balance in the ore heaps with wide catchment area, and the mining effluents have caused substantial metal and salting contamination of the receiving waterbodies. In our study, the impacts of metal-extracting bioheapleaching mine effluents on muscle and liver element concentrations, body condition, liver and testes mass, and sperm count and motility of male perch …

To incinerate or not? - Effects of incineration on the concentrations of heavy metals and leaching efficiency of post-precipitated sewage sludge (RAVITA™).

The major element and heavy metal concentrations of post-precipitated sewage sludge (PPS) and its ash residue (PPA) were determined using microwave digestion followed by inductively coupled plasma optical emission spectrometry (ICP-OES) and mass spectrometry (ICP-MS). To the best of our knowledge, this has not been previously done. In both PPS and PPA the heavy metal concentrations were clearly below the average concentrations than those encountered in sewage sludge in Europe. The leaching efficiency of the metal (Al/ Fe) used as a precipitation agent from post-precipitated sludge and its ash residue with phosphoric acid was also investigated with previously optimized leaching conditions. T…

Lumbriculus variegatus (Annelida) biological responses and sediment sequential extractions indicate ecotoxicity of lake sediments contaminated by biomining.

Abstract We assessed potential ecotoxicity of lake sediments affected by biomining effluents in northeastern Finland. Growth, reproduction and behavior of the sediment-dwelling oligochaete Lumbriculus variegatus (Muller 1774) were used as ecotoxicity endpoints. Standardized chronic bioassays were used for growth and reproduction, and acute and chronic tests with Multispecies Freshwater Biomonitor (MFB) for behavior assessments. Sequential extractions were used to characterize metal bioavailability and exposure conditions in the sediments, which indicated mining-induced contamination gradients of S, Cu, Ni and U and also bioavailability gradients of S and Ni. Among the ecotoxicity endpoints,…

Tolerance of Whitefish (Coregonus Lavaretus) Early Life Stages to Manganese Sulfate is Affected by the Parents

European whitefish (Coregonus lavaretus) embryos and larvae were exposed to 6 different manganese sulfate (MnSO4) concentrations from fertilization to the 3-d-old larvae. The fertilization success, offspring survival, larval growth, yolk consumption, embryonic and larval Mn tissue concentrations, and transcript levels of detoxification-related genes were measured in the long-term incubation. A full factorial breeding design (4 females × 2 males) allowed examination of the significance of both female and male effects, as well as female–male interactions in conjunction with the MnSO4 exposure in terms of the observed endpoints. The MnSO4 exposure reduced the survival of the whitefish early li…

Treatment of leachate from MSWI bottom ash landfilling with anaerobic sulphate-reducing process

Abstract Removal of sulphate and toxic elements from the leachate of a field landfill lysimeter ( 112 m 3 ) , containing municipal solid waste incineration (MSWI) bottom ash, was studied. The leachate was treated in two parallel laboratory upflow anaerobic sludge blanket (UASB) reactors without and with ethanol as additional carbon source. With ethanol more than 65% of sulphate was removed, while without ethanol removal was negligible. The treatment removed Ba, Ca, Cu, Mn, Mo, Ni, Pb, Tl, Sb, Se, Sr, and Zn of the studied 35 trace and other elements. The sequential extraction of the reactor sludge at the end of runs confirmed that with a few exceptions (Ba, Ca, and Cu) the main mechanism by…

Toxicity of copper and zinc assessed with three different earthworm tests

Abstract At present, standardised earthworm acute toxicity and reproduction tests are used to assess the toxicity of heavy metal contaminated soils. These tests are, however, time-consuming, laborious and costly, and in addition, some sublethal responses may remain overlooked. Avoidance of metal contaminated soils by earthworms may be a useful parameter when assessing ecological risks with a low test effort. The objective of the present study was to find out whether the earthworm Aporrectodea tuberculata avoids soils simultaneously contaminated with Cu and Zn, and whether earlier exposure to metal-polluted soil affects its avoidance response. The aim was also to compare the sensitivity of t…

Determination of metal concentrations in certified plastic reference materials after small-size autoclave and microwave-assisted digestion followed with inductively coupled plasma optical emission spectrometry

Abstract The digestion methods for the determination of As, Cd, Cr, Pb, Sb, Sn and Zn concentrations in plastic samples using microwave-assisted digestion (MW-AD) and small-size autoclave digestion was developed. The certified polyethylene, polypropylene, polyvinyl chloride and acrylonitrile butadiene styrene certified reference materials were used in order to find digestion method working properly for several sample matrices. Efficiency of the digestion methods was evaluated by analyzing the residual carbon in digests by TOC analyzer. MW-AD using a mixture of 7 mL of HNO 3 and 3 mL of H 2 O 2 as a digestion solution resulted in excellent recoveries for As, Cd, Pb, Sb and Zn, and were in th…

Control of matrix interferences by multiple linear regression models in the determination of arsenic and lead concentrations in fly ashes by inductively coupled plasma optical emission spectrometry

A multiple linear regression technique was used to evaluate and correct the matrix interferences in the determination of As and Pb concentrations in fly ashes by inductively coupled plasma optical emission spectrometry. The direct determination of As and Pb in SRM 1633b by ICP-OES failed to obtain the certified concentrations, except in a couple of cases. However, it proved possible to use the multiple linear regression (MLR) technique to correct the determined concentrations to a satisfactory level. This method of correction is based on the multiple regression line obtained from the analysis of 19 synthetic mixtures of matrix and analyte elements (Al, As, Ca, Fe, Pb, and Si) at five concen…

Purification of recovered phosphoric acid by extracting aluminium with di-2-ethylhexyl phosphoric acid

AbstractThe extraction of aluminium from dilute phosphoric acid with di-2-ethylhexyl phosphoric acid (DEHPA) was optimized using response surface methodology. The optimization was based on the experimental three-level central composite face-centred design (CCF) and was conducted on real-life samples. The three variables included were pH, extractant concentration and aqueous to organic phase ratio (AO). Under the optimized conditions (pH 2.5, 0.6 M DEHPA and AO ratio 1:2), extraction efficiency of 99% for aluminium in four extraction stages is achieved. The purified phosphoric acid solution can then be utilized by the fertilizing industry. Stripping tests for organic phase loaded with alumin…

Toxicity of binary mixtures of Cu, Cr and As to the earthworm Eisenia andrei

AbstractChromated copper arsenate (CCA) mixtures were used in the past for wood preservation, leading to large scale soil contamination. This study aimed at contributing to the risk assessment of CCA-contaminated soils by assessing the toxicity of binary mixtures of copper, chromium and arsenic to the earthworm Eisenia andrei in OECD artificial soil. Mixture effects were related to reference models of Concentration Addition (CA) and Independent Action (IA) using the MIXTOX model, with effects being related to total and available (H2O and 0.01 M CaCl2 extractable) concentrations in the soil. Since only in mixtures with arsenic dose-related mortality occurred (LC50 92.5 mg/kg dry soil), it wa…

Ecological risks of an old wood impregnation mill: application of the triad approach.

Although many studies deal with the distribution and mobility of chromated copper arsenate (CCA) metals in soil, the ecotoxicity of CCA-contaminated soils is rarely studied. The Triad approach was applied to determine the ecological risks posed by a CCA mixture at a decommissioned wood impregnation mill in southern Finland. A combination of (1) chemical analyses; (2) toxicity tests with plants (aquatic: Lemna minor; terrestrial: Lactuca sativa), earthworms (Lumbricus rubellus), and enchytraeids (Enchytraeus albidus) conducted on contaminated soils, their aqueous extracts, and well water collected from the site; and (3) determination of the abundance of enchytraeids and nematodes and the bio…

CCDC 929057: Experimental Crystal Structure Determination

Related Article: Antti Riisiö, Ari Väisänen, and Reijo Sillanpää|2013|Inorg.Chem.|52|8591|doi:10.1021/ic400663y

CCDC 929056: Experimental Crystal Structure Determination

Related Article: Antti Riisiö, Ari Väisänen, and Reijo Sillanpää|2013|Inorg.Chem.|52|8591|doi:10.1021/ic400663y

CCDC 929058: Experimental Crystal Structure Determination

Related Article: Antti Riisiö, Ari Väisänen, and Reijo Sillanpää|2013|Inorg.Chem.|52|8591|doi:10.1021/ic400663y

CCDC 929054: Experimental Crystal Structure Determination

Related Article: Antti Riisiö, Ari Väisänen, and Reijo Sillanpää|2013|Inorg.Chem.|52|8591|doi:10.1021/ic400663y

CCDC 929055: Experimental Crystal Structure Determination

Related Article: Antti Riisiö, Ari Väisänen, and Reijo Sillanpää|2013|Inorg.Chem.|52|8591|doi:10.1021/ic400663y

CCDC 929053: Experimental Crystal Structure Determination

Related Article: Antti Riisiö, Ari Väisänen, and Reijo Sillanpää|2013|Inorg.Chem.|52|8591|doi:10.1021/ic400663y

The determination of antimony and arsenic concentrations in fly ash by hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES)

Hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES) was used in the determination of As and Sb concentrations in fly ash samples. The effect of sample pre-treatment reagents and measurement parameters used for hydride generation was evaluated. Due to memory effects observed, the appropriate read delay time was adjusted to 60 s resulting in RSDs 0.6% and 2.3% for As and Sb, respectively. The most suitable volumes of pre-reduction reagents for 10 mL of sample were 4 mL of KI/ascorbic acid (5%) and 6 mL of HCl (conc.). The determination of Sb was significantly interfered by HF, but the interference could be eliminated by adding 2 mL of saturated boric acid …

An ultrasound-assisted digestion method for the determination of toxic element concentrations in ash samples by inductively coupled plasma optical emission spectrometry

method of ultrasound-assisted digestion followed by inductively coupled plasma optical emission spectrometry (ICP-OES) used for the determination of toxic element concentrations (arsenic, barium, cobalt, copper, lead, nickel, strontium, vanadium and zinc) in ash samples was developed. All the measurements were performed in robust plasma conditions which were tested by measuring the Mg(II) 280.270 nm/Mg(I) 285.213 nm line intensity ratios. The highest line intensity ratios were observed when a nebulizer gas flow of 0.6 L minˉ¹, auxiliary gas flow of 0.2 L minˉ¹ and plasma power of 1400 W were used for radially viewed plasma. The analysis of SRM 1633b showed that the ultrasound-assisted metho…

Control of matrix interferences by multiple linear regression models in the determination of arsenic and lead concentrations in fly ashes by inductively coupled plasma optical emission spectrometry

A multiple linear regression technique was used to evaluate and correct the matrix interferences in the determination of As and Pb concentrations in fly ashes by inductively coupled plasma optical emission spectrometry. The direct determination of As and Pb in SRM 1633b by ICP-OES failed to obtain the certified concentrations, except in a couple of cases. However, it proved possible to use the multiple linear regression (MLR) technique to correct the determined concentrations to a satisfactory level. This method of correction is based on the multiple regression line obtained from the analysis of 19 synthetic mixtures of matrix and analyte elements (Al, As, Ca, Fe, Pb, and Si) at five concen…