Uptake of heavy metals by plants from airborne deposition and polluted soils

Selostus: Kasvien raskasmetallien otto ilmasta ja saastuneesta maasta

Heavy-metal pollution and remediation of forest soil around the Harjavalta Cu-Ni smelter, in SW Finland

Abstract

EDTA- and DTPA-functionalized silica gel and chitosan adsorbents for the removal of heavy metals from aqueous solutions

Adsorbents functionalized with chelating agents are effective in removal of heavy metals from aqueous solutions. Important properties of such adsorbents are high binding affinity as well as regenerability. In this study, aminopolycarboxylic acid, EDTA and DTPA, were immobilized on the surface of silica gel, chitosan, and their hybrid materials to achieve chelating adsorbents for heavy metals such as Co(II), Ni(II), Cd(II), and Pb(II). New knowledge about the adsorption properties of EDTA- and DTPA-functionalizedadsorbents was obtained. Experimental work showed the effectiveness, regenerability, and stability of the studied adsorbents. Both advantages and disadvantages of the adsorbents were evaluated. For example, the EDTA-functionalized chitosan-silica hybrid materials combined the benefits of the silica gel and chitosan while at the same time diminishing their observed drawbacks. Modeling of adsorption kinetics and isotherms is an important step in design process. Therefore, several kinetic and isotherm models were introduced and applied in this work. Important aspects such as effect of error function, data range, initial guess values, and linearization were discussed and investigated. The selection of the most suitable model was conducted by comparing the experimental and simulated data as well as evaluating the correspondence between the theory behind the model and properties of the adsorbent. In addition, modeling of two-component data was conducted using various extended isotherms. Modeling results for both one- and twocomponent systems supported each other. Finally, application testing of EDTA- and DTPA-functionalized adsorbents was conducted. The most important result was the applicability of DTPA-functionalized silica gel and chitosan in the capturing of Co(II) from its aqueous EDTA-chelate. Moreover, these adsorbents were efficient in various solution matrices. In addition, separation of Ni(II) from Co(II) and Ni(II) and Pb(II) from Co(II) and Cd(II) was observed in two- and multimetal systems. Lastly, prior to their analysis, EDTA- and DTPA-functionalized silica gels were successfully used to preconcentrate metal ions from both pure and salty waters

Feasibility of ASH DEC‐ process in treating sewage sludge and manure ash in Finland

In Finland the thermal treatment of sewage sludge has been moderate in 21th century. The reason has been the high moisture content of sludge. During 2005-2008, 97-99% of sewage sludge was utilized in landscaping and agriculture. However agricultural use has been during 2005-2007 less than 3 %. The aim of national waste management plan is that by 2016 100% of sludge is used either as soil amendment or energy. The most popular utilization method for manure is spreading it on arable land. The dry manures such as poultry manure and horse manure could also be used in incineration. The ashes could be used as fertilizers and while it is not suitable as a starter fertilizer, it is suitable in maintaining P levels in the soil. One of the main drivers for more efficient nutrient management is the eutrophication in lakes and the Baltic See. ASH DEC process can be used in concentrating phosphorus rich ashes while separating the heavy metals that could be included. ASH DEC process uses thermochemical treatment to produce renewable phosphate for fertilizer production. The process includes mixing of ashes and chlorine donors and subsequent treatment in rotary kiln for 20 min in temperature of 900 – 1 050 oC. The heavy metals evaporate and P-rich product is obtained. The toxic substances are retained in air pollution control system in form of mixed metal hydroxides. The aim of conducting this study is to estimate the potential of ASH DEC process in treating phosphorus rich ashes in Finland. The masses considered in are sewage sludge, dry manure from horses, and poultry and liquid pig manure. To date the usual treatment method for sewage sludge in Finland is composting or anaerobic digestion. Part of the amount of produced sewage sludge (800 kt/a fresh mass and 160 kt/a TS) could also be incinerated and the residual ashes used in ASH DEC process. Incinerating only manure can be economically difficult to manage because the incineration of manure is in Finland considered as waste incineration. Getting a permit for waste incineration is difficult and also small scale waste incineration is too expensive. The manure could act as an additional feedstock in counties with high density of animal husbandry where the land area might not be enough for spreading of manure. Now when the manure acts as a supplementary feedstock beside sludge, the ash can’t be used directly as fertilizer. Then it could be used in ASH DEC process. The perquisite is that the manure producers could pay for the incineration, which might prove problematic.

Hydrometallurgical recovery of valuable metals from secondary raw materials

Wastes and side streams in the mining industry and different anthropogenic wastes often contain valuable metals in such concentrations their recovery may be economically viable. These raw materials are collectively called secondary raw materials. The recovery of metals from these materials is also environmentally favorable, since many of the metals, for example heavy metals, are hazardous to the environment. This has been noticed in legislative bodies, and strict regulations for handling both mining and anthropogenic wastes have been developed, mainly in the last decade. In the mining and metallurgy industry, important secondary raw materials include, for example, steelmaking dusts (recoverable metals e.g. Zn and Mo), zinc plant residues (Ag, Au, Ga, Ge, In) and waste slurry from Bayer process alumina production (Ga, REE, Ti, V). From anthropogenic wastes, waste electrical and electronic equipment (WEEE), among them LCD screens and fluorescent lamps, are clearly the most important from a metals recovery point of view. Metals that are commonly recovered from WEEE include, for example, Ag, Au, Cu, Pd and Pt. In LCD screens indium, and in fluorescent lamps, REEs, are possible target metals. Hydrometallurgical processing routes are highly suitable for the treatment of complex and/or low grade raw materials, as secondary raw materials often are. These solid or liquid raw materials often contain large amounts of base metals, for example. Thus, in order to recover valuable metals, with small concentrations, highly selective separation methods, such as hydrometallurgical routes, are needed. In addition, hydrometallurgical processes are also seen as more environmental friendly, and they have lower energy consumption, when compared to pyrometallurgical processes. In this thesis, solvent extraction and ion exchange are the most important hydrometallurgical separation methods studied. Solvent extraction is a mainstream unit operation in the metallurgical industry for all kinds of metals, but for ion exchange, practical applications are not as widespread. However, ion exchange is known to be particularly suitable for dilute feed solutions and complex separation tasks, which makes it a viable option, especially for processing secondary raw materials. Recovering valuable metals was studied with five different raw materials, which included liquid and solid side streams from metallurgical industries and WEEE. Recovery of high purity (99.7%) In, from LCD screens, was achieved by leaching with H2SO4, extracting In and Sn to D2EHPA, and selectively stripping In to HCl. In was also concentrated in the solvent extraction stage from 44 mg/L to 6.5 g/L. Ge was recovered as a side product from two different base metal process liquors with Nmethylglucamine functional chelating ion exchange resin (IRA-743). Based on equilibrium and dynamic modeling, a mechanism for this moderately complex adsorption process was suggested. Eu and Y were leached with high yields (91 and 83%) by 2 M H2SO4 from a fluorescent lamp precipitate of waste treatment plant. The waste also contained significant amounts of other REEs such as Gd and Tb, but these were not leached with common mineral acids in ambient conditions. Zn was selectively leached over Fe from steelmaking dusts with a controlled acidic leaching method, in which the pH did not go below, but was held close as possible to, 3. Mo was also present in the other studied dust, and was leached with pure water more effectively than with the acidic methods. Good yield and selectivity in the solvent extraction of Zn was achieved by D2EHPA. However, Fe needs to be eliminated in advance, either by the controlled leaching method or, for example, by precipitation. 100% Pure Mo/Cr product was achieved with quaternary ammonium salt (Aliquat 336) directly from the water leachate, without pH adjustment (pH 13.7). A Mo/Cr mixture was also obtained from H2SO4 leachates with hydroxyoxime LIX 84-I and trioctylamine (TOA), but the purities were 70% at most. However with Aliquat 336, again an over 99% pure mixture was obtained. High selectivity for Mo over Cr was not achieved with any of the studied reagents. Ag-NaCl solution was purified from divalent impurity metals by aminomethylphosphonium functional Lewatit TP-260 ion exchange resin. A novel preconditioning method, named controlled partial neutralization, with conjugate bases of weak organic acids, was used to control the pH in the column to avoid capacity losses or precipitations. Counter-current SMB was shown to be a better process configuration than either batch column operation or the cross-current operation conventionally used in the metallurgical industry. The raw materials used in this thesis were also evaluated from an economic point of view, and the precipitate from a waste fluorescent lamp treatment process was clearly shown to be the most promising.

Arseeni ja elohopea maaperässä ja vesistöissä

Maapallon väestön kasvaessa ja tarpeen makealle vedelle, ruualle ja viljelymaalle noustessa on tärkeää alkaa kiinnittää entistä tarkemmin huomiota vesistöjen ja maaperän saastumiseen myrkyllisillä raskasmetalleilla. Erityisesti elohopea ja arseeni, jotka jo nyt vaikuttavat heikentävästi miljoonien ihmisten elämään eri puolilla maapalloa, on syytä ottaa huolelliseen tarkkailuun. Raskasmetallien päästölähteet voidaan jakaa kahteen luokkaan, luonnollisiin ja ihmisperäisiin. Ihmisperäisiin päästölähteisiin voidaan vaikuttaa muun muassa teollisuutta ja liikennettä koskevalla lainsäädännöllä. Luonnollisiin päästölähteisiin vaikuttaminen on huomattavasti haastavampaa, mutta niiden haittaa ihmisille on mahdollista pienentää muun muassa parempien vedenpuhdistustekniikoiden avulla. Tämän työn kirjallisuusosassa tullaan esittelemään erityyppisiä luonnossa esiintyviä arseenin ja elohopean yhdisteitä, suurimpia arseenin ja elohopean päästölähteitä, sekä näiden raskasmetallien haitallisia terveysvaikutuksia. Kokeellisessa osassa tullaan keskittymään arseenin analysointiin nestemäisistä näytteistä. Näytteinä käytettiin tuntemattomilta kaatopaikoilta otettuja suotovesinäytteitä, sekä Pien-Saimaan pintavesinäytteitä. Analyyseihin on käytetty ICP-AES laitteistoa sekä kapillaarielektroforeesia.

Treatment of Fe-containing Acid Mine Waters in Fixed Bed Adsorption Column with Calcite Side-Stone

The acid mining drainage is considered the most significant environmental pollution problem around the world for the extensive formation acidic leachates containing heavy metals. Adsorption is widely used methods in water treatment due to it easy operation and the availability of a wide variety of commercial adsorbent (low cost). The primary goal of this thesis was to investigate the efficiency of neutralizing agents, CaCO3 and CaSiO3, and metal adsorption materials with unmodified limestone from Company Nordkalk Oy. In addition to this, the side materials of limestone mining were tested for iron adsorption from acidic model solution. This study was executed at Lappeenranta University of Technology, Finland. The work utilised fixed-bed adsorption column as the main equipment and large fluidized column. Atomic absorption spectroscopy (AAS) and x-ray diffraction (XRD) was used to determine ferric removal and the composition of material respectively. The results suggest a high potential for the studied materials to be used a low cost adsorbents in acid mine drainage treatment. From the two studied adsorbents, the FS material was more suitable than the Gotland material. Based on the findings, it is recommended that further studies might include detailed analysis of Gotland materials.

Environmental Challenges in the Joint Border Area of Norway, Finland and Russia

This report examines the human impact on the subarctic environment of the joint border area of Norway, Finland and Russia. The aim is to present the current state and recent changes that have taken place in the region. The main threat to the environment is the Pechenganikel mining and metallurgical industrial combine in the towns of Nikel and Zapolyarny in the Kola Peninsula. Emissions from this complex include high levels of heavy metals, persistent organic pollutants and sulfur dioxide. Pollution, along with climate change, water level regulation and other anthropogenic effects, has affected the aquatic ecosystems in the joint border area. The main heavy metals in the area are copper and nickel, the highest concentrations of which are measured near the combine. Direct discharge of sewage into the river continues and airborne heavy metal particles are also deposited to areas farther away. Climate changeinduced increase in temperature and precipitation in the Kola Peninsula is evident. Water level regulation with seven hydropower plants in the Pasvik River have changed it into a series of lakes and lake-like reservoirs. This report discusses modelling, which was enabled to estimate the effect of climate change on Lake Inarijärvi and the Pasvik River hydrology, water level fluctuation and ecology and to follow the sulfur dioxide emissions emitted from the Pechenganikel. Effects of pollution on the nature and concentrations of the main pollutants were studied and climate change in the border area and its effects on the ecology were estimated. Also the effects of water level regulation on the ecological status of the aquatic ecosystems were addressed.

Termodesorptiolaitoksen päästöt

Tässä diplomityössä tutkittiin pilaantuneen maan puhdistamiseen käytettävän termodesorptiolaitoksen päästöjä ilmaan. Tarkasteluun otettiin raskasmetallit ja happamista päästöistä rikkidioksidi (SO2) ja vetykloridi (HCl).Näiden haitta-aineiden puhdistusta tutkittiin mittaamalla niiden pitoisuuksia ennen ja jälkeen kaasunpuhdistuksen. Tutkimuksessa havaittiin raskasmetallien sekä happamien yhdisteiden puhdistuvan käytössä olevalla tekniikalla erittäin hyvin. Viranomaisten asettamat päästöraja-arvot alitettiinselvästi.

Removal of Cadmium, Lead and Arsenic from Water by Lactic Acid Bacteria

A number of contaminants such as arsenic, cadmium and lead are released into the environment from natural and anthropogenic sources contaminating food and water. Chronic oral ingestion of arsenic, cadmium and lead is associated with adverse effects in the skin, internal organs and nervous system. In addition to conventional methods, biosorption using inactivated biomasses of algae, fungi and bacteria has been introduced as a novel method for decontamination of toxic metals from water. The aim of this work was to evaluate the applicability of lactic acid bacteria as tools for heavy metal removal from water and characterize their properties for further development of a biofilter. The results established that in addition to removal of mycotoxins, cyanotoxins and heterocyclic amines, lactic acid bacteria have a capacity to bind cationic heavy metals, cadmium and lead. The binding was found to be dependent on the bacterial strain and pH, and occurred rapidly on the bacterial surface, but was reduced in the presence of other cationic metals. The data demonstrates that the metals were bound by electrostatic interactions to cell wall components. Transmission electron micrographs showed the presence of lead deposits on the surface of biomass used in the lead binding studies, indicating involvement of another uptake/binding mechanism. The most efficient strains bound up to 55 mg Cd and 176 mg Pb / g dry biomass. A low removal of anionic As(V) was also observed after chemical modification of the cell wall. Full desorption of bound cadmium and lead using either dilute HNO₃ or EDTA established the reversibility of binding. Removal of both metals was significantly reduced when biomass regenerated with EDTA was used. Biomass regenerated with dilute HNO3 retained its cadmium binding capacity well, but lead binding was reduced. The results established that the cadmium and lead binding capacity of lactic acid bacteria, and factors affecting it, are similar to what has been previously observed for other biomasses used for the same purpose. However, lactic acid bacteria have a capacity to remove other aqueous contaminants such as cyanotoxins, which may give them an additional advantage over the other alternatives. Further studies focusing on immobilization of biomass and the removal of several contaminants simultaneously using immobilized bacteria are required.

Lentotuhkan fraktiointi sähkösuodattimella ja Ion Blast -menetelmällä

Diplomityö on osa YTI-tutkimuskeskuksessa vuosina 2002 - 2004 toteutettavaa Jätekompostit rakeiksi tuhkaseostuksella -käyttöarvon parantaminen -projektia. Työssä tutkittiin Etelä-Savon Energia Oy:n Pursialan voimalaitoksen lentotuhkan fraktioimista voimalaitoksen nykyisellä 3-kenttäisellä sähkösuodattimella ja pilot-mittakaavaisella Ion Blast -koelaitteistolla. Sähkösuodattimen koeajojen aikana muuteltiin sen ajotapaa mm. CBO -suhteen ja maksimijänniteasetuksen avulla. Ion Blast -koelaitteistolla tutkittiin mahdollisuuksia voimalaitoksen lentotuhkan puhdistamiseksi raskasmetalleista. Lentotuhkan hyötykäyttöä vaikeuttaa sen raskasmetallipitoisuuksien suuri vaihtelu. Ongelmallisin raskasmetalli puuperäisessä lentotuhkassa on kadmium, jonka lannoitelainsäädännön raja-arvo on tällä hetkellä 3 mg/kg. Sähkösuodattimella tehtyjen fraktiointikokeiden perusteella voidaan todeta raskasmetallipitoisuuksien olevan pienimmillään sähkösuodattimen 1-kentässä ja suurimmillaan 3-kentässä. Tämä johtuu siitä, että 1-kenttään kerääntyy hiukkaskooltaan suurimmat lentotuhkahiukkaset ja 3-kentässä on mukana enemmän pienhiukkasia sisältävää tuhkaa. Lannoitteeksi menevän tuhkan Cd-pitoisuutta voidaan vähentää parhaimmillaan jopa 70 % sähkösuodattimella fraktioimalla. Muiden raskasmetallien pitoisuudet eivät vähene aivan yhtä paljon. Sähkösuodattimella voidaan tulosten perusteella fraktioida lentotuhkaa. Sähkösuodattimella ei kuitenkaan voida varmasti saavuttaa alle 3 mg/kg Cd-pitoisuuksia polttoaineen laadunvaihtelun vuoksi. Ion Blast -koelaitteiston tulokset tukevat sähkösuodattimella tehtyjä kokeita. Erottimen jännitteen kasvaessa raskasmetalleja sisältävien hiukkasten erotusaste kasvaa. Ion Blast -laitteistolla tehdyissä kokeissa myös Cd-pitoisuus oli korkeimmillaan pienimmän raeluokan hiukkasissa ja laski sitten raeluokan suurentuessa. Ion Blast -laitteisto ei kuitenkaan sellaisenaan ole hyvä fraktiointiin. Se on liian tehokas, jolloin se puhdistaa tehokkaasti myös raskasmetalleja sisältävät pienhiukkaset. Jos laitetta aiotaan käyttää fraktiointiin, tulisi sen rakennetta muuttaa.