| 11. |
- Gustafsson, Jon Petter, et al.
(author)
-
Modeling salt-dependent proton binding by organic soils with the MICA-Donnan and Stockholm Humic models
- 2005
-
In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 39:14, s. 5372-5377
-
Journal article (peer-reviewed)abstract
- Models are available for simulations of proton dissociation and cation binding by natural organic matter; two examples are the NICA-Donnan and Stockholm Humic (SHM) models. To model proton and metal binding, it is necessary to properly account for the ionic strength dependence of proton dissociation. In previous applications of the models for soils it was assumed that the electrostatic interactions for solid-phase humic substances were the same as in solution;this assumption was recently challenged. Therefore, we reanalyzed previously published acid-base titrations of acid-washed Sphagnum peat, and we produced additional data sets for two Sphagnum peats and two Spodosol Oe horizons. For the soil suspensions, the original NICA-Donnan and SHM models, which were developed for dissolved humic substances, underestimated the observed salt dependence considerably. When a fixed Donnan volume of 1 L kg(-1) for humic substances in the solid phase was used, the NICA-Donnan model fits were much improved. Also for SHM, slight changes produced improved model fits. The models also produced acceptable simulations of the dissolved Ca, Mg, and Cd concentrations, provided that cation selectivity was introduced. In conclusion, the proposed extensions to the NICA-Donnan and SHM models were shown to predict the salt dependence of solid-phase humic substances more satisfactorily than earlier model versions.
|
|
| 12. |
- Gustafsson, Jon Petter, et al.
(author)
-
Modeller för spridning av metaller från mark till vatten
- 2007
-
Reports (other academic/artistic)abstract
- Att förstå och kvantifiera metallers spridning i mark och grundvatten är en central del av riskbedömningen för förorenad mark. För att göra detta krävs kunskap om hur stor utlakningen av den aktuella metallen är från föroreningskällan samt hur den lokala hydrologin, geologin och geokemin påverkar spridningen till en näraliggande recipient genom bl.a. utspädning och fördröjning. Olika typer av spridningsmodeller kan användas beroende på föroreningens typ, förorenat media (mark, grundvatten, ytvatten, sediment), hydrogeologiska förhållanden samt inte minst beroende på vilken typ av frågor som man vill besvara. De allra enklaste spridningsmodeller som används idag för förorenade områden (t.ex. för beräkning av riktvärden för mark) tar inte hänsyn till någon bindning till den fasta fasen - sorption - i marken och därmed ingen fördröjning under grundvattentransporten. Istället uppskattas endast den utspädning som sker när förorenat vatten blandas upp med annat grundvatten. Nästa typ av modeller, som i framtiden bör föredras framför de enklaste modellerna, använder sig av advektionsdispersionsekvationen med antagande om linjär sorption (Kd-värden). Dessamodeller kan beräkna halter och utsläpp som funktion av tid och rum. Två näraliggande områden där utvecklingen av spridningsmodeller kommit relativt långt, och där det finns erfarenheter av intresse att hämta i samband med riskbedömning av förorenad mark, är säkerhetsanalyser av kärnavfallsförvar i berg, samt simulering av pesticidutlakning från åkermark. Fördelningskoefficienten mellan jord och lösning, det s.k. Kd-värdet, är avcentral betydelse i riskbedömningen för att korrekt kunna förutsäga spridningen av en förorening genom markvatten- och grundvattenzonen. Man bör dock skilja denna fördelningskoefficient från den som beskriver utlakningen från en föroreningskälla grundad på totalhalten av föroreningen; denna koefficient bör kallas Ktot. Den senare kan användas för att bestämma den lösta koncentrationen för en förorening vid föroreningskällan (Cw i riktvärdesmodellen), men bör inte användas för bedömning av spridningsrisk till grund- och ytvatten. Då ”egna” Kd-värden för spridning uppskattas i samband med platsspecifika riskbedömningar, bör dessa utgå antingen från den geokemiskt aktiva mängden bestämd från en extraktion / tillgänglighetstest eller från ett sorptionstest. Utvidgade Freundlichuttryck kan, rätt använda, vara ett enkelt men ändå betydligt förbättrat redskap för att uppskatta Kd-värden för spridning av vissa metaller i ytliga jordlager. I rapporten har flera publicerade modeller byggda på utvidgade Freundlichuttryck utvärderats. Av de undersökta modellerna framgår det att Sauvés modell är den som ligger närmast till hands att rekommenderas för uppskattningar av Kd-värden i ytliga jordlager för Cd, Cu, Ni, Pb och Zn. För att använda Sauvés modell behövs uppskattningar av pH, halt organiskt kol, och av antingen koncentrationen löst metall i vattenfas eller halt fastlagd (potentiellt lakbar) metall. På sikt kan mer termodynamiskt grundande så kallade multiytmodeller vara ett intressant alternativ för många oorganiska föroreningar; dessa har dock i dagens läge alltför låg användarvänlighet. I djupare jordlager i t.ex. grundvattenzonen kan inte Sauvés modell användas. Inte heller är det lämpligt att använda t.ex. Naturvårdsverkets onservativa antaganden om Kd-värden för den generella riktvärdesmodellen, eftersom dessa endast är konservativa för ytliga jordhorisonter och riskerar att överskatta Kd-värden för grundvattenzonen. Det är angeläget med mer forskning för att belysa djupare jordlagers sorptionsegenskaper. Vid beräkningar av transport i jordar är det viktigt att ta hänsyn till att endast en del av den totala mängden jord är tillgänglig för sorption. Vid simuleringar med advektions-dispersionsmodellen kan fördröjningsfaktorn justeras för att kompensera för den begränsade sorptionskapaciteten, men även andra mer komplicerat uppbyggda modeller finns som även beräknar utbytet mellan delar av jorden med mobilt respektive immobilt vatten. En bra spridningsmodell omfattar: (i) en tidsberoende beskrivning av utlakningsförloppet från en föroreningskälla; (ii) en transportmodell som tar hänsyn till heterogeniteter och till att endast vissa delar av jorden är tillgänglig för sorption; (iii) hänsynstagande till halt löst organiskt material vilket kan forcera utlakningen för vissa metaller (t.ex. Cu, Hg), (iv) beskrivning av sorption av föroreningar med hjälp av utvidgade Freundlichuttryck.
|
|
| 13. |
- Gustafsson, Jon-Petter
(author)
-
Modelling metal sorption in soil
- 2009. - 1
-
In: Modelling of pollutants in complex environmental systems. - St Albans : ILM Publications. - 9781906799007
-
Book chapter (peer-reviewed)
|
|
| 14. |
- Gustafsson, Jon Petter, et al.
(author)
-
Phosphate removal by mineral-based sorbents used in filters for small-scale wastewater treatment
- 2008
-
In: Water Research. - : Elsevier. - 0043-1354 .- 1879-2448. ; 42:1-2, s. 189-197
-
Journal article (peer-reviewed)abstract
- The mineral-based sorbents Filtra P, Polonite (R), natural wollastonite and water-cooled blast furnace slag (WCBFS) were studied in terms of their PO4 removal performance. Results from a long-term column experiment showed that both Filtra P and Polonite (R) removed > 95% of PO4 from the applied synthetic solution, and that the used filter materials had accumulated several (1.9-19) g kg(-1) P. Phosphorus was removed also by natural wollastonite and WCBFS, but these materials were less efficient. Batch experiments on the used materials showed that the solubility PO4 was considerably larger than the one expected for crystalline Ca phosphates such as hydroxyapatite, and results from investigations with attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) on the Filtra P material showed that the formed P phase was not crystalline. These evidence suggest that a soluble amorphous tricalcium phosphate (ATCP) was formed in the mineral-based sorbents; the apparent solubility constant on dissolution was estimated to log K-s = -27.94 ( 0.31) at 21 degrees C. However, since only up to 18% of the accumulated PO4 was readily dissolved in the experiments, it cannot be excluded that part of the phosphorus had crystallized to slightly less soluble phases. In conclusion, Filtra P and Polonite are two promising mineral-based sorbents for phosphorus removal, and at least part of the accumulated phosphorus is present in a soluble form, readily available to plants.
|
|
| 15. |
- Gustafsson, Jon Petter, et al.
(author)
-
Towards a consistent geochemical model for prediction of uranium(VI) removal from groundwater by ferrihydrite
- 2009
-
In: Applied Geochemistry. - Oxford : Pergamon Press. - 0883-2927 .- 1872-9134. ; 24:3, s. 454-462
-
Journal article (peer-reviewed)abstract
- Uranium(VI), which is often elevated in granitoidic groundwaters, is known to adsorb strongly to Fe (hydr)oxides under certain conditions. This process can be used in water treatment to remove U(VI). To develop a consistent geochemical model for U(VI) adsorption to ferrihydrite, batch experiments were performed and previous data sets reviewed to optimize a set of surface complexation constants using the 3-plane CD-MUSIC model. To consider the effect of dissolved organic matter (DOM) on U(VI) speciation, new parameters for the Stockholm Humic Model (SHM) were optimized using previously published data. The model, which was constrained from available X-ray absorption fine structure (EXAFS) spectroscopy evidence, fitted the data well when the surface sites were divided into low- and high-affinity binding sites. Application of the model concept to other published data sets revealed differences in the reactivity of different ferrihydrites towards U(VI). Use of the optimized SHM parameters for U(VI)-DOM complexation showed that this process is important for U(VI) speciation at low pH. However in neutral to alkaline waters with substantial carbonate present, Ca–U–CO3 complexes predominate. The calibrated geochemical model was used to simulate U(VI) adsorption to ferrihydrite for a hypothetical groundwater in the presence of several competitive ions. The results showed that U(VI) adsorption was strong between pH 5 and 8. Also near the calcite saturation limit, where U(VI) adsorption was weakest according to the model, the adsorption percentage was predicted to be >80%. Hence U(VI) adsorption to ferrihydrite-containing sorbents may be used as a method to bring down U(VI) concentrations to acceptable levels in groundwater.
|
|
| 16. |
- Khai, Nguyen Manh, et al.
(author)
-
Modeling of metal binding in tropical Fluvisols and Acrisols treated with biosolids and wastewater
- 2008
-
In: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 70:8, s. 1338-1346
-
Journal article (peer-reviewed)abstract
- There is growing concern about the accumulation of metals in tropical agricultural soils. In this study, experimental results from batch studies were used to test whether multi-surface geochemical models could describe metal binding in selected Vietnamese soils. The multi-surface models considered metal binding to iron hydroxides (using the diffuse layer model), organic matter (Stockholm Humic model and NICA-Donnan model), and phyllosilicate clay (Gaines-Thomas equation) as well as complexation to dissolved organic and inorganic ligands in the solution phase. We found that for total dissolved Cd, Cu and Zn the two multi-surface models being tested provided very good model fits for all soils, as evidenced by low root-mean square errors between model predictions and observations. These results suggest that organic matter is an important sorbent for many metals in these soils. However, poor fits were obtained for Cr(III), Mn and Pb for all soils. The study also suggests that the pH is the main factor that controls the solubility of metals in tropical Fluvisols and Acrisols subjected to application of biosolids and wastewater, and that advanced multi-surface models can be used to simulate the binding and release of many trace metals.
|
|
| 17. |
- Kleja, D. B., et al.
(author)
-
Assessment of isotopically exchangeable Al in soil materials using Al-26 tracer
- 2005
-
In: Geochimica et Cosmochimica Acta. - : Elsevier BV. - 0016-7037 .- 1872-9533. ; 69:22, s. 5263-5277
-
Journal article (peer-reviewed)abstract
- The solubility of aluminium (Al) in many acidic soils is controlled by complexation reactions with soil organic matter. In such soils, Al solubility is theoretically a function of the pool size of active Al, i.e., the total amount of Al that equilibrates with the sod solution within a defined period of time. To date, no reliable measurements of active Al in soil materials exist. In this study, we determined the isotopically exchangeable pool of Al (E-A1) as an operationally defined assessment of active Al in acidic mineral soils. The suitability of CuCl2 and pyrophosphate (Na4P2O7) as extractants for active Al was also evaluated. Eleven samples, mostly from spodic B horizons, were spiked with carrier-free Al-26 and equilibrated for different time periods (1-756 h). The size of the Al pool with which the Al-26 tracer exchanged increased with time during the whole experimental period. Thus, contact time between solid and solution phases needs to be defined when assessing the active Al pool. Values of E-A1 obtained after I to 5 d of equilibration were equal to the amount of CuCl2 extractable Al, but considerably smaller than the Na4P2O7-extractable pool. Equilibration times greater than 5 d resulted in CuCl2 extractable Al concentrations that under-estimated the active Al pool. Three of the investigated samples were rich in imogolite-type materials (ITM). In these samples, 30-50 % of the added Al-26 rapidly became associated with soil constituents in forms that could not be extracted by Na4P2O7, indicating that a part of ITM may be in a dynamic state.
|
|
| 18. |
- Linde, Mats, et al.
(author)
-
Effects of changed soil conditions on the mobility of trace metals in moderately contaminated urban soils
- 2007
-
In: Water, Air and Soil Pollution. - : Springer Science and Business Media LLC. - 0049-6979 .- 1573-2932. ; 183:04-jan, s. 69-83
-
Journal article (peer-reviewed)abstract
- Changes in the soil chemical environment can be expected to increase the leaching of trace metals bound in soils. In this study the mobility of trace metals was monitored in a column experiment for two contaminated urban soils. Four different treatments were used (i.e. rain, acid rain, salt and bark). Leachates were analysed for pH, dissolved organic carbon (DOC) and for seven trace metals (cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn)). The salt treatment produced the lowest pH values (between 5 and 6) in the effluent whereas the DOC concentration was largest in the bark treatment (40-140 mg L-1) and smallest in the salt and acid treatments (7-40 mg L-1). Cadmium, Ni and Zn were mainly mobilised in the salt treatment, whereas the bark treatments produced the highest concentrations of Cu and Pb. The concentrations of Cu, Cr, and Hg were strongly correlated with DOC (r(2) = 0.90, 0.91 and 0.96, respectively). A multi-surface geochemical model (SHM-DLM) produced values for metal dissolution that were usually of the correct magnitude. For Pb, however, the model was not successful indicating that the retention of this metal was stronger than assumed in the model. For all metals, the SHM-DLM model predicted that soil organic matter was the most important sorbent, although for Pb and Cr(III) ferrihydrite was also important and accounted for between 15 and 50% of the binding. The results confirm the central role of DOC for the mobilization of Cu, Cr, Hg and Pb in contaminated soils.
|
|
| 19. |
- Nehrenheim, Emma, et al.
(author)
-
Kinetic sorption modelling of Cu, Ni, Zn, Pb and Cr ions to pine bark and blast furnace slag by using batch experiments
- 2008
-
In: Bioresource Technology. - : Elsevier BV. - 0960-8524 .- 1873-2976. ; 99:6, s. 1571-1577
-
Journal article (peer-reviewed)abstract
- Storm water and landfill leachate can both contain significant amounts of toxic metals such as Zn, Cu, Pb, Cr and Ni. Pine bark and blast furnace slag are both residual waste products that have shown a large potential for metal removal from contaminated water. There are however many variables that must be optimized in order to achieve efficient metal retention. One of these variables is the time of which the solution is in contact with each unit of filter material. Metal sorption was studied in two laboratory experiments to improve the knowledge of the effects of contact time. The results showed that pine bark was generally more efficient than blast furnace slag when the metal concentrations were relatively small, whereas blast furnace slag sorbed most metals to a larger extent at increased metal loads. In addition, sorption to blast furnace slag was found to be faster than metal binding to pine bark. A pseudo-second-order kinetic model was able to describe the data well within 1000 s of reaction time.
|
|
| 20. |
- Olsson, Susanna, et al.
(author)
-
Copper(II) binding to dissolved organic matter fractions in municipal solid waste incinerator bottom ash leachate
- 2007
-
In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 41:12, s. 4286-4291
-
Journal article (peer-reviewed)abstract
- Information on Cu speciation in municipal solid waste incineration (MSWI) bottom ash leachate is needed for Cu leaching predictions and toxicity estimates. The complexation of Cu with dissolved organic matter (DOM) in leachates from a stored MSWI bottom ash was studied potentiometrically using a Cu-ion selective electrode. More than 95% of the copper was bound to DOM in the hydrophilic fraction of the leachate, indicating that the hydrophilic acids contribute to Cu complex formation. The hydrophilic acids constituted 58% of the dissolved organic carbon in the ash leachate. Comparisons between experimental results and speciation calculations with the NICA-Donnan model and the Stockholm humic model indicated differences between the ash DOM and the natural DOM for which the models have been calibrated. The ratio of carboxylic binding sites to phenolic binding sites was 2 times larger in ash DOM, and the Cu-binding affinity of the former was stronger than accounted for by the generic Cu-binding parameters. The Cu-binding affinity of the phenolic sites, on the other hand, was weaker. When these parameters were adjusted, a good description of the experimental data was obtained.
|
|
