Bernd Nowack

Environmental chemistry of phosphonates

Phosphonates are anthropogenic complexing agents containing one or more C-PO(OH)(2) groups. They are used in numerous technical and industrial applications as chelating agents and scale inhibitors. Phosphonates have properties that differentiate them from other chelating agents and that greatly affect their environmental behavior. Phosphonates have a very strong interaction with surfaces, which results in a significant removal in technical and natural systems. Due to this strong adsorption, little or no remobilization of metals is expected. No biodegradation of phosphonates during water treatment is observed but photodegradation of the Fe(III)-complexes is rapid. Aminopolyphosphonates are also rapidly oxidized in the presence of Mn(II) and oxygen and stable breakdown products are formed that have been detected in wastewater. The lack of information about phosphonates in the environment is linked to analytical problems of their determination at trace concentrations in natural waters. Further method development is urgently needed in this area, including speciation of these compounds. With the current knowledge on speciation, we can conclude that phosphonates are mainly present as Ca and Mg-complexes in natural waters and therefore do not affect metal speciation or transport.

Root-zone modeling of heavy metal uptake and leaching in the presence of organic ligands

We present a mechanistic model which describes root uptake and leaching of heavy metals in the plant root zone, accounting for solution- and surface-complexation, (kinetic) mineral dissolution, heavy metal diffusion towards the root, root uptake, root exudation, ligand degradation and convective-dispersive transport of the soluble species. The model was used to simulate the influence of EDTA addition on Cu transport and plant uptake and the effect of oxalate exudation by roots on Cu transport and bioavailability using parameter values from the literature. In the simulations we assumed that free Cu2+ is the bioavailable form. Under slightly acidic conditions (pH 6) the model predicted that EDTA stabilizes Cu while at a slightly alkaline pH (pH 7.5), EDTA mobilizes Cu. The addition of EDTA approximately halved the cumulative Cu uptake after 360 days at pH 4.5, and reduced the uptake by a factor of 100 and 1000 at pH 6 and 7.5, respectively. Although the total dissolved concentration was increased, plant uptake was reduced by the formation of bio-inavailable complexes. The exudation of oxalate resulted in a decrease of the Cu concentration breaking through below the root zone, due to sorption of Cu-oxalate. In the presence of dissolved organic carbon (DOC), the exudation of oxalate increased Cu leaching considerably at pH 6 and 7.5. In the absence of DOC, the exudation of oxalate reduced Cu uptake due to the formation and adsorption of Cu-oxalate on goethite surface sites. Exudation of oxalate in the presence of DOC resulted in a further decrease of Cu uptake. Oxalate gradually takes over from DOC in binding Cu due to simultaneous production of oxalate and leaching of DOC. The simulations show that addition or exudation of ligands does not necessarily increase the solubility, transport and bioavailability of metals. Depending on the conditions (mainly the pH), also reduced transport and uptake can be observed, either by formation of ternary surface complexes or reduction of free metal concentration. The model can be easily extended to include further processes.

Verification and intercomparison of reactive transport codes to describe root-uptake

Several mathematical models have been developed to simulate processes and inter- actions in the plant rhizosphere. Most of these models are based on a rather simplified descrip- tion of the soil chemistry and interactions of plant roots in the rhizosphere. In particular the feed- back loops between exudation, water and solute uptake are mostly not considered, although their importance in the bioavailability of mineral ele- ments for plants has been demonstrated. The aim of this work was to evaluate three existing coupled speciation-transport tools to model rhi- zosphere processes. In the field of hydrogeo- chemistry, such computational tools have been developed to describe acid-base and redox reac- tions, complexation and ion exchange, adsorption and precipitation of chemical species in soils and aquifers using thermodynamic and kinetic rela- tionships. We implemented and tested a simple rhizosphere model with three geochemical com- putational tools (ORCHESTRA, MIN3P, and PHREEQC). The first step was an accuracy

Metal fractionation in a contaminated soil after reforestation: Temporal changes versus spatial variability

In a lysimeter experiment, topsoils were polluted with filter dust from a non-ferrous metal smelter and then planted with trees. Sequential extractions were used to follow the changes in metal fractionation of Cu, Zn, Cd, and Pb over 42 months. Plant-free and uncontaminated soils served as reference. In the contaminated and planted soils, the largest changes in speciation occurred within the first 6 months. The relative amounts of certain metal fractions were linearly related to each other, indicating systematic redistribution between fractions. The results indicate that under natural conditions with high heterogeneity in total metal contents spatial differences are more important than temporal variations in determining the fractionation and solubility of metals in contaminated soils. In the absence of plants soils exhibited a completely different fractionation 30 months after pollution, with much higher proportions in the more refractory phases. This suggests that plant activity kept the metals in a more soluble form.

Cu and Zn mobilization in soil columns percolated by different irrigation solutions.

We investigated the effects of different concentrations of nitrate and ammonium in irrigation water on the mobilization of Zn and Cu in repacked soil columns with a metal-polluted topsoil and unpolluted subsoils over two and a half years. Soil solution samples were collected by suction cups installed at vertical distances of a few centimeters and analyzed for dissolved organic carbon (DOC), Cu, and Zn (total and labile). During high N treatments the pH decreased and the presence of exchangeable cations resulted in Zn mobilization from the surface soil. The nitrogen input stimulated the biological activity, which affected both concentration and characteristics of DOC and consequently Cu speciation. Metal leaching through the boundary between the polluted topsoil and the unpolluted subsoils increased soil-bound and dissolved metals within the uppermost 2cm in the subsoils. Our study shows that agricultural activities involving nitrogen fertilization can have a strong influence on metal leaching and speciation.

Decrease of labile Zn and Cd in the rhizosphere of hyperaccumulating Thlaspi caerulescens with time

By using a rhizobox micro-suction cup technique we studied in-situ mobilization and complexation of Zn and Cd in the rhizosphere of non-hyperaccumulating Thlaspi perfoliatum and two different Thlaspi caerulescens ecotypes, one of them hyperaccumulating Zn, the other Zn and Cd. The dynamic fraction (free metal ions and small labile complexes) of Zn and Cd decreased with time in the rhizosphere solution of the respective hyperaccumulating T. caerulescens ecotypes, and at the end of the experiment, it was significantly smaller than in the other treatments. Furthermore, the rhizosphere solutions of the T. caerulescens ecotypes exhibited a higher UV absorptivity than the solution of the T. perfoliatum rhizosphere and the plant-free soil. Based on our findings we suggest that mobile and labile metal-dissolved soil organic matter complexes play a key role in the rapid replenishment of available metal pools in the rhizosphere of hyperaccumulating T. caerulescens ecotypes, postulated earlier.

Aminopolyphosphonate removal during wastewater treatment

Phosphonates are used in large quantities in industry and household products as scale inhibitors and chelating agents. They are not biodegraded during wastewater treatment but are removed by adsorption processes. Field measurements from different wastewater treatment plants affirm that they are removed almost completely during wastewater treatment. Adsorption of nitrilotrismethylenephosphonic acid onto activated sludge, amorphous iron oxide and humic acids (HAs) was studied under controlled conditions. The adsorption onto HAs decreases sharply with increasing pH with negligible adsorption at pH above 6.5. Adsorption onto amorphous iron oxide follows a Langmuir behavior. The presence of 1 mM Ca doubles the maximum surface capacity at pH 7. Adsorption onto activated sludge is not very pH sensitive and is explained to a large extent by adsorption onto amorphous iron oxides, but the contribution of organic matter or other mineral phases cannot be ruled out.

Uptake of Zn and Fe by Wheat (Triticum aestivum var. Greina) and Transfer to the Grains in the Presence of Chelating Agents (Ethylenediaminedisuccinic Acid and Ethylenediaminetetraacetic Acid)

A way to decrease iron and zinc deficiency in humans is to biofortify foods by increasing the bioavailable contents in these elements. The aim of this work was to study if chelating agents could be used to increase the capture of Fe and Zn by wheat grains. Zn and/or Fe in combination with the chelating agents ethylenediaminedisuccinic acid (EDDS) or ethylenediaminetetraacetic acid (EDTA) were added at various times (i.e., at flower head formation, anthesis, and postanthesis) to spring wheat ( Triticum aestivum var. Greina) grown in nutrient solution. Treatments lasted for 2 weeks, and the plants were harvested at grain maturity. The shoots of treated plants accumulated higher Zn and/or Fe concentrations than untreated plants, depending on the treatment. The plants also accumulated significant concentrations of EDDS or EDTA in their shoots. Elevated Zn and Fe concentrations in the shoots did in most cases not lead to significantly higher Zn and Fe concentrations in the grains. The grains of plants treated with EDDS during flower head formation accumulated elevated Fe and Zn concentrations but at the cost of a reduction in yield. The control plants transferred higher percentages of Fe and Zn from the shoot into the grain than the treated plants. This indicates that EDTA and EDDS inhibited in most cases the translocation of Fe and Zn from the shoots into the grains. The amounts of EDDS and EDTA found in the grains of treated plants were very small. This indicates that there was little transfer of the chelates into the symplast and that the apoplastic pathway, which is important for the transport of chelants into the shoots, is efficiently blocked between shoots and seeds.

Determination of phosphonic acid breakdown products by high-performance liquid chromatography after derivatization

A new HPLC method for the determination of oxidative breakdown products of aminopolyphosphonates is presented. The phosphonate nitrilotrismethylenephosphonic (NTMP) acid undergoes catalytic oxidation by molecular oxygen in the presence of manganese(II). The two diphosphonates iminodimethylenephosphonic acid (IDMP) and formyliminodimethylenephosphonic acid (FIDMP) are formed. The analytical method employs the derivatization of the aldehyde group in FIDMP by 2,4-dinitrophenylhydrazine and of the imine group in IDMP by 9-fluorenyl methylchloroformate. The two derivatives are quantified in separate runs using the same acidic phosphate-acetonitrile eluent with detection at 370 nm for FIDMP and 260 nm for IDMP. The detection limit for FIDMP is 0.01 microM, for IDMP 0.02 microM. The method is suitable for the determination of the breakdown products in wastewater.

In-situ Method for Analyzing the Long-Term Behavior of Particulate Metal Phases in Soils

Soils can act as a sink for anthropogenic and naturally released heavy metals. Among these are heavy metal oxides and sulfides, which are emitted e.g. by mining industry and metal smelting. The dissolution and transformation behavior of these heavy metal phases specifies their fate in the soil and determines whether the metals become bioavailable or could contaminate the groundwater. To gain more information about these dissolution reactions in soils, in-situ methods are needed. We present here a method to fix particulate metal phases on an inert support. This method allows us to expose and recover metal phases in the environment under controlled conditions.