Birnessite-induced mechanochemical degradation of 2,4-dichlorophenol.

DCP (2,4-dichlorophenol) is the key-intermediate in the synthesis of some widely used pesticides and is an EPA priority pollutant. The mechanochemical breakdown of DCP loaded on birnessite (δ-MnO2), montmorillonite saturated with Na(+) or Cu(2+) and hematite was investigated. Mechanical force was applied by grinding of mixtures of DCP and the minerals, using mortar and pestle. Grinding of DCP for 5 min with the montmorillonites or with hematite resulted in negligible degradation during grinding, while grinding with birnessite induced the immediate degradation of 90% of the loaded DCP. Incubation for 24h after grinding did result in up to 30% degradation of the DCP loaded on the other minerals tested. HPLC and LC-MS analysis revealed that the transformation of DCP yielded oligomerization products as well as partial dechlorination. DCP degradation on birnessite was accompanied with a substantial increase in the extractability of manganese from the mineral into an acidic aqueous solution, indicating that Mn(IV) in the mineral transformed into Mn(II) and that birnessite served as an electron acceptor in the transformation. The oligomerization and partial dechlorination brought about by grinding, suggest a reduction in bioavailability and toxicity.

Uptake of cadmium by hydroponically grown, mature Eucalyptus camaldulensis saplings and the effect of organic ligands.

The potential suitability of Eucalyptus camaldulensis for Cd phytoextraction was tested in a hydroponic study. Saplings were exposed to 4.5 and 89 microM Cd for one month, with and without EDTA and s,s-EDDS at 0.1, 1, and 5 mM. The saplings' growth was not affected at the 4.5 microM Cd concentration, yet it decreased 3-fold at 89 microM, and almost all the Cd taken up was immobilized in the roots, reaching 360 and 5300 mg Cd kg(-1), respectively (approximately 75% of which was non-washable in acid). The respective Cd root-to-shoot translocation factors were 0.14 and approximately 5*10(-4). At 0.1 mM concentration, EDTA and EDDS had no effect or even a positive effect on the saplings growth. This was reversed at 1 mM, and the chelants became lethal at the 5 mM concentration. At 89 microM Cd in the growth medium, 0.1 mM EDTA increased Cd translocation into the shoots by almost 10-fold, however it strongly reduced Cd content inside the roots. This hydroponic study indicates the feasibility of E. camaldulensis use for cleanup Cd-contaminated soils at environmental concentrations, both for site stabilization (phytostabilization) and gradual remediation (phytoextraction). EDTA was shown to be much more efficient in enhancing Cd translocation than s,s-EDDS.

"Phytoscreening": the use of trees for discovering subsurface contamination by VOCs.

We tested the possibility of using tree cores to detect unknown subsurface contamination by chlorinated volatile organic compounds (Cl-VOCs) and petroleum hydrocarbons, a method we term "phytoscreening". The scope and limitations of the method include the following: (i) a number of widespread Cl-VOC contaminants are readily found in tree cores, although those with very high vapor pressures or low boiling points may be absent; (ii) volatile petroleum hydrocarbons were notwell-expressed in tree cores; (iii) trees should be sampled during active evapotranspiration and from directions that are well exposed to sunlight; (iv) there is not necessarily a direct correlation between concentrations measured in tree cores and those in the subsurface; (v) detection of a contaminant in a tree core indicates that the subsurface is contaminated with the pollutant; (vi) many possible causes of false negatives may be predicted and avoided. We sampled trees at 13 random locations in the Tel Aviv metropolitan area and identified Cl-VOCs in tree coresfromthree locations. Subsequently, subsurface contamination at all three sites was confirmed. Phytoscreening is a simple, fast, noninvasive, and inexpensive screening method for detecting subsurface contamination, and is particularly useful in urban settings where conventional methods are difficult and expensive to employ.

Retention of trace metals by solidified/stabilized wastes: assessment of long-term metal release.

Toxic elements found in wastes may have a negative impact on the environment, especially through the contamination of groundwater and plants. To reduce their mobility and availability, French regulations mandate the solidification and stabilization of toxic wastes. Many methods to stabilize and solidify wastes exist, among them the Ecofix process which employs low cost materials and consists of mixing wastes with lime, aluminum hydroxide, and silica. To evaluate the long-term behavior of solidified/stabilized (S/S) samples, their alteration under saturated conditions was studied in a water extractor, a Soxhlet-like device, used to follow the weathering of rocks. Kinetic measurements have shown that the release of Fe, Pb, Cd, Cr, and Cu was very slow, indicating a strong retention of these elements by the S/S materials prepared by the Ecofix process. To elucidate the mechanisms of retention of the trace metals, the mineral phases that existed in the S/S samples throughout and at the end of the extraction runs were studied by X-ray diffraction and by infrared and nuclear magnetic resonance spectroscopies. Scanning electron microscopic (SEM) examinations and electron microprobe analyses of the S/S samples were also performed at different stages of weathering. These observations revealed that assorted calcium silicate hydrates (C-S-H) were the predominant phases in the S/S preparations and that gradual alterations occurred in the structure of the investigated materials. The overall Ca/Si ratio of the C-S-H phases decreased as the enhanced alteration progressed. Although trace metals in oxide, hydroxide, and carbonate forms were found in the S/S materials, the bulk of the trace metals was incorporated in the matrix of the C-S-H phases.

Sorption of copper and zinc to the plasma membrane of wheat root.

Sorption of Cu(2+) and Zn(2+) to the plasma membrane (PM) of wheat root (Triticum aestivum L cv. Scout 66) vesicles was measured at different pH values and in the presence of organic acids and other metals. The results were analyzed using a Gouy-Chapman-Stem model for competitive sorption (binding and electrostatic attraction) to a negative binding site. The binding constants for the two investigated cations as evaluated from the sorption experiments were 5 M(-1) for Zn(2+) and 400 M(-1) for Cu(2+). Thus, the sorption affinity of Cu(2+) to the PM is considerably larger than that of Ca(2+), Mg(2+) or Zn(2+). The greater binding affinity of Cu(2+) was confirmed by experiments in which competition with La(3+) for sorption sites was followed. The amount of sorbed Cu(2+) decreased with increasing K(+), Ca(2+), or La(3+) concentrations, suggesting that all these cations competed with Cu(2+) for sorption at the PM binding sites, albeit with considerable differences among these cations in effectiveness as competitors with Cu(2+). The sorption of Cu(2+) and Zn(2+) to the PM decreased in the presence of citric acid or malic acid. Citric acid (as well as pH) affected the sorption of Cu(2+) or Zn(2+) to PM more strongly then did malic acid.

Copper and zinc speciation in the solution of a soil-sludge mixture.

Only a small fraction of the transition metals content in sludge-amended soils is soluble, and yet this fraction is a major contributor to the mobility and bioavailability of the metals. The chemical species of zinc (Zn) and copper (Cu) in the soluble fractions of soil-sludge mixtures were characterized with respect to their charge, molecular weight, and stoichiometry using ion exchange resin and gel chromatography procedures. The change in the metals' species with time after sludge application was followed for 100 d. Copper in the water extracts of the sludge-sand mixtures was found almost exclusively in low molecular weight (below 1000 Da) complexes. Higher molecular weight (around 2500 Da) dissolved organic carbon (DOC) was present in the extracts as well, but this DOC fraction exhibited little complexation. Copper was present in the extracts mainly as negatively charged species throughout the incubation period, and zinc tended to form zwitter ions. As incubation progressed, the relative content of positively charged Zn in solution increased. Complexation capacity of DOC in sludge water extract, extrapolated to infinite dilution, was 8.75 mM Ca g(-1) DOC. When the complexation capacity of the extract is near saturation, a mean Cu-DOC complex can be defined. It consists of 1.9 Cu atoms attached to DOC species containing 5.6 C atoms. Thus, the organic Cu complexes consist primarily of about two Cu ions attached to DOC species containing only five or six C atoms. Amino acids and small peptides or polycarboxylic acids, such as citric acid, thus may be important complexing agents of the metal.

Direct quantification of unadsorbed viruses in suspensions of adsorbing colloids with the enzyme-linked immunosorbent assay.

Quantification of two plant viruses in suspensions of homoionic Ca-bentonite was conducted by applying to the enzyme-linked immunosorbent assay plates either the virus-clay mixture (direct method) or the supernatant obtained after the clay was allowed to settle (classic method). Both methods showed a similar dependence of free virus content on clay concentration. A higher content at equilibrium was measured for both viruses by the direct method. The advantage of using the direct over the classic method is discussed.