Mechanisms governing the leaching of soil metals as a result of disposal of olive mill wastewater on agricultural soils.

Olive mill wastewater (OMWW) is an acidic, saline, and organic matter-rich aqueous byproduct of olive oil production that is usually disposed of by spreading on agricultural soils. This study tested whether spreading OMWW can release indigenous soil metals (Fe, Mn, Cu and Zn) through pH, redox, and DOM complexation-related mechanisms, using three agricultural soils having different textures and chemical properties, and controlled pH and redox conditions (pH5.6 or 8.4; ORP from -200 to +250mV). Comparison treatments included a solution having the same salt content and composition as OMWW but lacking OM, and deionized water (DW). In all three soils and under all pH and redox conditions, the model salt solution and DW treatments solubilized considerably fewer metal cations than did OMWW. Overall, the primary factor in metals release from the soils by OMWW was the DOM fraction. pH, redox and soil type played secondary but important roles in solubilization of the various metals. pH had a major impact on Mn leaching but no impact on Fe and Cu leaching. Conversely, redox did not affect Mn leaching, but lower redox conditions contributed to elevated release of both Fe and Cu. For the most part, released metals were sourced from water soluble, exchangeable, easily reducible, and moderately reducible soil metals pools. Fe, Mn and Cu released from the soils by OMWW featured mainly as metal-organic complexes, and OMWW generally caused Zn precipitation in the soils. Soils rich in clay and organic matter under reduced pH and low redox conditions released substantially more metal cations than did a sand-rich soil. Spreading OMWW may result in sequestration of essential micronutrients like Zn, and increased availability of other micronutrients such as Fe, Mn and Cu.

Impact of spreading olive mill waste water on agricultural soils for leaching of metal micronutrients and cations.

Olive mill waste water (OMWW) is an acidic (pH 4-5), saline (EC âˆ¼ 5-10 mS cm-1), blackish-red aqueous byproduct of the three phase olive oil production process, with a high chemical oxygen demand (COD) of up to 220,000 mg L-1. OMWW is conventionally disposed of by uncontrolled dumping into the environment or by semi-controlled spreading on agricultural soils. It was hypothesized that spreading such liquids on agricultural soils could result in the release and mobilization of indigenous soil metals. The effect of OMWW spreading on leaching of metal cations (Na, K, Mg, Mn, Fe, Cu, Zn) was tested in four non-contaminated agricultural soils having different textures (sand, clay loam, clay, and loam) and chemical properties. While the OMWW contributed metals to the soil solution, it also mobilized indigenous soil metals as a function of soil clay content, cation exchange capacity (CEC), and soil pH-buffer capacity. Leaching of soil-originated metals from the sandy soil was substantially greater than from the loam and clay soils, while the clay loam was enriched with metals derived from the OMWW. These trends were attributed to cation exchange and organic-metal complex formation. The organic matter fraction of OMWW forms complexes with metal cations; these complexes may be mobile or precipitate, depending on the soil chemical and physical environment.

"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.

Competitive uptake of trichloroethene and 1,1,1-trichloroethane by Eucalyptus camaldulensis seedlings and wood.

The efficient use of trees for taking up volatile organic compounds (VOCs) from the subsurface for remedial and screening purposes is hampered because many poorly quantified co-occurring processes affect VOC concentrations in the tree, the most basic of which are VOC sorption and uptake by roots. Toward understanding the dominant sorption mechanisms, uptake of trichloroethene (TCE) and 1,1,1-trichloroethane (TCA) by Eucalyptus camaldulensis seedlings was studied in both single-solute and bi-solute experiments. Single-solute and bi-solute sorption experiments on wood from a mature Eucalyptus camaldulensis specimen were also carried out. Competition between TCE and TCA for sorption sites was found in both seedling uptake and wood sorption experiments, indicating that partitioning is not the sole mechanism governing compound interactions in these systems. The nonlinear single-solute sorption isotherms on wood were fit by a dual-mode model including partitioning and Langmuir terms. The dual-mode model calculated parameters were consistent with the results of the bi-solute sorption experiments. As a consequence of competitive sorption processes, uptake of individual compounds may be lower than expected when multiple VOC contaminants are present in the subsurface.

Hydration-assisted sorption of a probe organic compound at different Peat hydration levels: the link solvation model.

Sorption isotherms of phenol on Pahokee Peat as model natural organic matter(NOM) have been measured at different partial NOM hydrations (water activities). Sorption at a given phenol solution concentration is substantially smaller in the lower water activity systems than in higher water activity systems, reaching a sorption maximum at an intermediate water activity. Such cooperative phenol uptake at interim water activities as a result of NOM hydration (hydration-assisted sorption) is predicted by the link solvation model (LSM), whereby water enhances the disruption of the noncovalently cross-linked NOM structure, creating new sorption sites. The LSM is herein extended to account for the observed direct relationship between isotherm linearity and water activity. The extended LSM provides an excellent description of phenol sorption isotherm data at nine different NOM hydration levels with a single set of three unique parameters. The successful fit of the LSM supports the conceptual model of creation of new sorption sites for sorbate molecules in the hydrated organic matter sorbent, accompanied by competition for those new sites by water molecules at high water activities.