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.

Soil spreading of liquid olive mill processing wastes impacts leaching of adsorbed terbuthylazine.

Olive mill waste water (OMWW) is a major byproduct of the three phase olive oil production process. OMWW has high acidity (pH âˆ¼ 4-5), high salt content (EC âˆ¼ 5-10 mS cm(-1)), extremely high biological and chemical oxygen demand (BOD and COD up to 100,000 and 220,000 mg L(-1), respectively), and also high concentrations of organic compounds such as phenols and polyphenols. As a result, OMWW cannot be freely discharged into domestic wastewater treatment plants, but on-site treatment is very expensive and not sufficiently effective. Uses for OMWW such as agricultural recycling and co-composting were found to be impractical or expensive. Thus, OMWW is frequently spread on agricultural land for disposal. However, excessive or uncontrolled spreading of such organic-rich and saline wastewater could have many deleterious effects on soil quality, including salinization, phytotoxicity, or contaminant movement. The impact of OMWW on the leaching of adsorbed terbuthylazine, a soil-applied herbicide, was tested in four soils of varying physical and chemical properties. Although terbuthylazine solubility in OMWW is significantly higher than in water, leaching of adsorbed terbuthylazine from OMWW-treated soils was less than from control treatments. Low soil organic carbon and clay contents were major factors that contributed to reduced terbuthylazine leaching after soil treatment with OMWW.

pH-dependent mineral release and surface properties of cornstraw biochar: agronomic implications.

Surface charge and pH-dependent nutrient release properties of cornstraw biochar were examined to elucidate its potential agronomic benefits. Kinetics of element release was characterized by rapid H(+) consumption and rapid, pH-dependent P, Ca, and Mg release, followed by zero-order H(+) consumption and mineral dissolution reactions. Initial K release was not pH-dependent, nor was it followed by a zero-order reaction at any pH. Rapid and constant rate P releases were significant, having the potential to substitute substantial proportions of P fertilizer. K releases were also significant and may replace conventional K fertilizers, however, not long-term plant demand. The cation exchange capacity (CEC) of the biochar leached with a mild acidic solution increased linearly from 179 to 888 mmol(c) (kg C)(-1) over a pH range of 4-8, while the anion exchange capacity of 154 mmol(c) (kg C)(-1) was constant over the same pH range. Since native soil organic constituents have much higher CEC values (average 2800 mmol(c) (kg C)(-1) at pH 7), improved soil fertility as a result of enhanced cation retention by the biochar probably will be favorable only in sandy and low organic matter soils, unless surface oxidation during aging significantly increases its CEC.

Hydration-influenced sorption of organic compounds by model and atmospheric humic-like substances (HULIS).

Atmospheric humic-like substances (HULIS) constitute a major fraction of the water soluble organic carbon of aerosol particles. We investigated sorption and desorption of water and two model organic contaminants (toluene and benzyl alcohol) on HULIS and a standard humic substance (Suwannee River fulvic acid; SRFA) under varying relative humidity using a quartz crystal microbalance. Simultaneous sorption of water and benzyl alcohol (capable of specific interactions like hydrogen bonding or charge transfer) on HULIS and SRFA shows significant, humidity-dependent, cooperative sorption at intermediate water activity, as well as a dependence of sorption distribution coefficient on the wetting-drying pathway. In contrast, sorption of toluene (capable of only nonspecific interactions) was humidity-independent. Atmospheric HULIS is thus found to have several sorption features in common with terrestrial and aquatic humic substances and soil organic matter. These features are consistent with the link solvation model (LSM), whereby water assists in cooperative sorption of specifically interacting compounds by the organic matter sorbent, and subsequent changes in sorbent structure result in sorption hysteresis. Sorption of compounds capable of only nonspecific interactions is unaffected by hydration status. Such sorption features can lead to considerable uncertainty in predicting and modeling transport of organic pollutants in the atmosphere.

"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.

Soil water repellency induced by long-term irrigation with treated sewage effluent.

This study describes soil water repellency developed under prolonged irrigation with treated sewage effluent in a semiarid environment. Soil surface layer (0-5 cm) and soil profile (0-50 cm) transects were sampled at a high resolution at the close of the irrigation season and rainy winter season. Samples from 0- to 5-cm transects were subdivided into 1-cm slices to obtain fine scale resolution of repellency and organic matter distribution. Extreme to severe soil water repellency in the 0- to 5-cm soil surface layer persisted throughout the 2-yr study period in the effluent-irrigated Shamouti orange [Citrus sinensis (L.) Osbeck cv. Shamouti] orchard plot. Nearby Shamouti orange plots irrigated with tap water were either nonrepellent or only somewhat repellent. Repellency was very variable spatially and with depth, appearing in vertically oriented "repellency tongues." Temporal and spatial variability in repellency in the uppermost 5-cm soil surface layer was not related to seasonality, soil moisture content, or soil organic matter content. Nonuniform distribution of soil moisture and fingered flow were observed in the soil profile after both seasons, demonstrating that the repellent layer had a persistent effect on water flow in the soil profile. A lack of correlation between bulk density and volumetric water content in the soil profile demonstrates that the observed nonuniform spatial distribution of moisture results from preferential flow and not heterogeneity in soil properties. Soil water repellency can adversely affect agricultural production, cause contamination of underlying ground water resources, and result in excessive runoff and soil erosion.

Competitive sorption of organic contaminants in chalk.

In the Negev desert, Israel, a chemical industrial complex is located over fractured Eocene chalk formations where transfer of water and solutes between fracture voids and matrix pores affects migration of contaminants in the fractures due to diffusion into the chalk matrix. This study tests sorption and sorption competition between contaminants in the chalk matrix to make it possible to evaluate the potential for contaminant attenuation during transport in fractures. Single solute sorption isotherms on chalk matrix material for five common contaminants (m-xylene, ametryn, 1,2-dichloroethane, phenanthrene, and 2,4,6-tribromophenol) were found to be nonlinear, as confirmed in plots of Kd versus initial solution concentration. Over the studied concentration ranges, m-xylene Kd varied by more than a factor of 100, ametryn Kd by a factor of 4, 1,2-dichloroethane Kd by more than a factor of 3, phenanthrene Kd by about a factor of 2, and 2,4,6-tribromophenol Kd by a factor of 10. It was earlier found that sorption is to the organic matter component of the chalk matrix and not to the mineral phases (Chemosphere 44 (2001) 1121). Nonlinear sorption isotherms indicate that there is at least some finite sorption domain. Bi-solute competition experiments with 2,4,6-tribromophenol as the competitor were designed to explore the nature of the finite sorption domain. All of the isotherms in the bi-solute experiments are more linear than in the single solute experiments, as confirmed by smaller variations in Kd as a function of initial solution concentration. For both m-xylene and ametryn, there is a small nonlinear component or domain that was apparently not susceptible to competition by 2,4,6-tribromophenol. The nonlinear sorption domain(s) is best expressed at low solution concentrations. Inert-solvent-normalized single and bi-solute sorption isotherms demonstrate that ametryn undergoes specific force interactions with the chalk sorbent. The volume percent of phenanthrene sorbed at the liquid solubility limit is calculated to be 13% v:v in both the single and bi-solute experiments. This value exceeds what may be reasonably interpreted as partitioning of phenanthrene into organic matter, despite the relative linearity of the phenanthrene sorption isotherm (compared with other compounds) in both single and bi-solute systems.

Retardation of organic contaminants in natural fractures in chalk.

Transport of a conservative compound and two sorbing compounds through fractured chalk was studied using flow-through columns consisting of chalk cores with a single subvertical fracture. Two types of chalk matrix were compared, an oxidized white chalk with low organic carbon content (0.2%), and a gray chalk with a higher organic carbon content (1.3%). Initial rapid breakthrough followed by a delayed approach to a relative concentration of unity for the conservative compound (2,6-difluorobenzoic acid [DFBA]) was clear evidence for diffusion into the porous chalk matrix. Matrix diffusion of DFBA was apparently much greater in the gray chalk columns than in the white chalk columns. Breakthrough curves (BTCs) of the sorbing compounds (2,4,6-tribromophenol [TBP] and ametryn [AME]) were retarded in all cases as compared to the conservative compound. Sorption retardation was far greater in the gray chalk as compared with the white chalk, in good agreement with results from batch sorption experiments. BTCs for the conservative compound were relatively nonhysteretic for both white and gray chalk columns. In contrast, BTCs for the sorbing compounds were hysteretic in all cases, demonstrating that sorption was not at equilibrium before desorption began. These experiments suggest that on a field scale, transport of contaminants through fractures in chalk and other fractured porous media will be attenuated by diffusion and sorption into the matrix.

Suitability of dye-clay complexes for removal of non-ionic organic compounds from aqueous solutions.

Aqueous sorption of phenol, atrazine and naphthalene was measured on complexes formed from Na-montmorillonite (Fischer bentonite) and the organic cationic dyes crystal violet and rhodamine-B. Sorption isotherms were found to be non-linear. This agrees well with the rigid nature of the dye-clay organic coverage, which provides a finite surface for adsorption. High values of organic carbon-normalized distribution coefficients reached 20,000-25,000 for atrazine on rhodamine-B-montmorillonite, 7000 for atrazine on crystal violet-montmorillonite, and 1500 for phenol on crystal violet-montmorillonite. As such, dye-clays may significantly extend the variety of organoclay sorbents that effectively reduce aqueous concentrations of non-ionic organic compounds.

Enhanced transport of pesticides in a field trial with treated sewage sludge.

This study was designed to provide high-density data on spatial distribution of three herbicides with different physiochemical characteristics in a sludge-amended and non-amended control field over the course of an irrigation season. The field experiment was carried out on a sandy loam Hamra Red Mediterranean soil (Rhodoxeralf) at Bet Dagan, Israel. After a single 50 mm irrigation event, the mean centers of mass (COM) in the control field were at 15.6, 14.9, and 17 cm for bromacil, atrazine and terbuthylazine, respectively; in the sludge-amended field, mean COMs were at 28.8, 31.2, and 34.1 cm, respectively. After 500 mm of irrigation in the control field, the COM depth distribution of the three pesticides was inversely correlated with octanol-water (Kow) distribution coefficients and soil sorption coefficients (Koc), and positively correlated with aqueous solubilities. After 500 mm irrigation in the sludge-amended field, the mean terbuthylazine COM was at 19.8 cm versus 13.8 cm for the control field, demonstrating a sustained enhanced effect on terbuthylazine transport. Downward transport of atrazine was also enhanced by sludge amendment, albeit less than terbuthylazine. Bromacil was preferentially accumulated in the upper soil layers of the sludge-amended field as compared with the control field after 500 mm irrigation. The enhanced transport of all three pesticides in the sludge-amended field after a single irrigation event is attributed to development of preferential flow pathways around hydrophobic clods of sludge. Enhanced transport of terbuthylazine, and to a lesser extent, atrazine, throughout the irrigation season, is attributed to their transport as complexes with dissolved, colloidal and suspended organic matter derived from sludge degradation.

Sorption of organic contaminants in a fractured chalk formation.

Sorption capability of bedrock components from a fractured chalk province was evaluated using ametryn, phenanthrene, m-xylene, 2,4,6-tribromophenol, and 1,2-dichloroethane. Sorption isotherms for the four aromatic compounds were nonlinear on gray (unoxidized) chalk. Over the studied solution ranges, the distribution coefficient decreased by factor of 3 for phenanthrene and m-xylene, a factor 4 for ametryn, and by an order of magnitude for 2,4,6-tribromophenol. In contrast, 1,2-dichloroethane displayed a linear isotherm. The importance of polar interactions for ametryn sorption was evaluated by normalizing sorption to an "inert" solvent, n-hexane. n-Hexane-normalized sorption of ametryn was much greater than that of phenanthrene, presumably due to ametryn participation in hydrogen bonding interactions. In sharp contrast to sorption to gray chalk, sorption to white (oxidized) chalk is 100- to 1000-fold lower at any given solution concentration. The much greater sorption on gray chalk cannot be explained by specific surface area, clay content, or organic matter content; thus, the nature of the organic matter is considered to control sorption in the chalk samples. Gray chalk sorption capacity estimates for ametryn and 2,4,6-tribromophenol are similar, which, together with evidence of competition for sorption sites, suggests that the limited capacity sorption domain for both compounds is similar.

Solvation effect on organic compound interactions in soil organic matter.

We examine sorption of pyridine by soil organic matter (SOM) from different organic media including n-hexadecane, acetonitrile, acetone, and n-hexadecane mixtures with either acetonitrile or acetone and compare it with sorption from water. By using an activity-based comparison, we distinguish between solvent-assisted and solvent-competitive sorption behavior. Pyridine was selected because it forms strong complexes with phenolic and carboxylic groups, such that site interactions should dominate interactions in SOM. It is anticipated that pyridine sorption will be illustrative of the importance of disrupting strong interactions in a condensed, shrunken SOM phase for many organic compounds. It was generally found that activity-normalized pyridine uptake was assisted by polar solvent molecules rather than suppressed due to competition. An explanation is tendered on the basis of our earlier hypothesis of water-assisted disruption of polar SOM contacts. Certain polar moieties of dry SOM are unavailable for compound sorption due to strong interactions between them. By penetrating SOM structure, solvent molecules (and water) solvate (hydrate) polar moieties creating new sorption sites. Solvent molecules must solvate both moieties of the polar contact, such that the driving force for solvent-assisted sorption is solvation of the partner of the disrupted contact that does not directly interact with the sorbate.