Evaporation as the transport mechanism of metals in arid regions.

Soils of arid regions are exposed to drought and drastic temperature oscillations throughout the year. Transport mechanisms in these soils are therefore very different from the ones in temperate regions, where rain dictates the fate of most elements in soils. Due to the low rainfall and high evaporation rates in arid regions, groundwater quality is not threatened and all soil contamination issues tend to be overlooked. But if soil contamination happens, where do contaminants go? This study tests the hypothesis of upward metal movement in soils when evaporation is the main transport mechanism. Laboratory evaporation tests were carried out with heavy metal spiked Saudi soil, using circulation of air as the driving force (Fig. 1). Main results show that loamy soil retains heavy metals quite well while evaporation drives heavy metals to the surface of a sandy soil. Evaporation transports heavy metals upward in sandy soils of arid regions, making them accumulate at the soil surface. Sand being the dominating type of soil in arid regions, soils can then be a potential source of contaminated aerosols and atmospheric pollution - a transboundary problem. Some other repercussions for this problem are foreseen, such as the public ingestion or inhalation of dust.

Assessing PAH removal from clayey soil by means of electro-osmosis and electrodialysis.

Polycyclic aromatic hydrocarbons (PAH) are persistent and toxic contaminants which are difficult to remove from fine porous material like clayey soils. The present work aims at studying two electroremediation techniques for the removal of PAHs from a spiked natural silt soil from Saudi Arabia and a silty loam soil from The Netherlands which has been exposed to tar contamination for over 100 years. The two techniques at focus are electro-osmosis and electrodialysis. The latter is applied for the first time for the removal of PAH. The efficiency of the techniques is studied using these two soils, having been subjected to different PAH contact times. Two surfactants were used: the non-ionic surfactant Tween 80 and anionic surfactant sodium dodecyl sulphate (SDS) to aid desorption of PAHs from the soil. Results show a large discrepancy in the removal rates between spiked soil and long-term field contaminated soil, as expected. In spiked soil, electro-osmosis achieves up to 85% while electrodialysis accomplishes 68% PAH removal. In field contaminated soil, electro-osmosis results in 35% PAH removal whereas electrodialysis results in 79%. Short recommendations are derived for the up-scale of the two techniques.

Quantifying the effect of membrane potential in chemical osmosis across bentonite membranes by virtual short-circuiting.

Clay liners are charged membranes and show semipermeable behavior regarding the flow of fluids, electrical charge, chemicals and heat. At zero gradients of temperature and hydrostatic pressure, a salt concentration gradient across a compacted clay sample induces not only an osmotic flux of water and diffusion of salt across the membrane but also an electrical potential gradient, defined as membrane potential. Laboratory experiments were performed on commercially available bentonite samples in a rigid-wall permeameter connected to two electrically insulated fluid reservoirs filled with NaCl solutions of different concentrations and equipped with Ag/AgCl electrodes to measure the electrical potential gradient. The effect of membrane potential could be cancelled out by short-circuiting the clay with the so-called virtual shortcut. The potential gradient across the sample is brought to zero with a negative feedback circuit. It was observed that the water flux and the diffusion of Cl- were hindered by the occurrence of a membrane potential, indicating that an electroosmotic counterflow is induced. Flow parameters were calculated with modified coupled flow equations of irreversible thermodynamics. They were in excellent agreement with values reported in the literature. Comparing the method of short-circuiting with a study elsewhere, where the electrodes were physically short-circuited, it was shown that the virtual shortcut is more appropriate because physically short-circuiting induces additional effects that are attributed to the fluxes.

Dissolution kinetics of heavy metals in Dutch carbonate- and sulfide-rich freshwater sediments.

In two sulfide-rich freshwater sediments from the Biesbosch and Kromme Rijn River in the Netherlands differing in carbonate content and acid volatile sulfide (AVS) content, metal and sulfide dissolution kinetics were studied at different acid concentrations by varying both the procedure of acid addition and the extraction time. The establishment of equilibrium was monitored by measuring the pH in time, which reached a near constant value. The equilibrium pH was reached quickly when large amounts of acid were added and slowly when small amounts of acid were added. This observation was confirmed by the yield of extracted metals after either a 45-min or 24-h extraction over a pH range from 0 to 5. The pH factor seemed to be of more influence than time for the dissolution of metals. The amount of extracted metals was highly dependent on the metal itself due to its physico-chemical behavior. Although the sediments studied varied in carbonate content, acid volatile sulfide (AVS), and total metal content, the extracted fraction of metals compared with their total content in the sediment was similar for most metals. Finally, the AVS content as well as the ratio of simultaneously extracted metals (SEM; sum of Cd, Cu, Ni, Pb, and Zn) to AVS decreased with increasing pH. Because the SEM to AVS ratio may be used to set environmental quality criteria for the sediment compartment, this observation is of significance.

The effect of oxidation and acidification on the speciation of heavy metals in sulfide-rich freshwater sediments using a sequential extraction procedure.

The speciation of metals in a contaminated, anoxic, sulfide-rich, freshwater sediment was determined experimentally, using a sequential extraction procedure based on the method of Tessier et al. Taking into account the advantages and disadvantages of sequential extractions, the applied methodology allowed the investigation of the influence of aeration and acidification on the distribution of various metals in the sediment. Aeration caused Zn and Cd to be released from sulfides. Carbonates were partly dissolved by the oxidation process, causing mobilisation of Ca. Fe became less mobile owing to a stronger binding to organic matter. The speciation of K, Al, Ni, Pb and Mn and to a lesser extent of Cu was not affected by aeration. As a result of acidification of the aerated sediment, Ca, Mn, Ni, Zn and Cd became more mobile owing to the dissolution of carbonates.

Pesticide residues in groundwater in The Netherlands: state of observations and future directions of research.

In the first stage of a programme of sampling and analysis for pesticide residues in groundwater in The Netherlands, the upper groundwater below four vulnerable soils was analysed for nearly 2,5 years in eight sampling rounds. Of 18 compounds analysed, including some metabolites, 1,3-dichloropropene, aldicarb, ethoprophos dinoseb, metamitron, atrazine, desethyl- and desisopropylatrazine, metolachlor and ethylenethioureum were repeatedly detected in the groundwater in concentrations above 0.1 micrograms.dm-3, the limit for pesticides in drinking water set by the EC. These observations were made below fields with potatoe-, maize- and bulb flower culture, all on low-humic to moderately humic sandy soils. No residues were found below a cracked light clay on a sandy subsoil. On the locations sampled evidence was found for complete in situ removal in the upper groundwater of 1,3-dichloropropene, high persistence of aldicarb residues and partial in situ degradation of dinoseb.