The impact of olive mill wastewater on soil properties, nutrient and heavy metal availability - A study case from Syrian vertisols.

Olive oil mill wastewater (OMW) is an environmental concern in olive oil producers' regions due to its use in agricultural soils as an organic amendment. However, OMW can also be used as organic fertilizer due to their high organic matter and nutrient levels, but its use, when it occurs without environmental management, can cause serious environmental implications for soils and waters. This work evaluated the impact of different OMW levels on a set of physicochemical parameters from an agricultural vertisol where wheat grew (Triticum aestivum L var. Douma 1). A set of physicochemical parameters were conducted before adding different levels of OMW (0, 5, 10 and 15 L m-2) at two soil depths (0-30 and 30-60 cm) and for the two growing seasons to determine: i) the effect of OMW treatments on the studied physicochemical soil properties (bulk density, soil porosity, soil pH, electrical conductivity and organic matter), ii) available primary (N, P, K) and secondary macronutrients (Ca, Mg and Na), ii) micronutrients (Cu Fe, Mn and Zn), and iv) available heavy metals (Cd and Pb). The results indicated that soil physicochemical parameters were slightly improved, mainly due to improvement in organic matter, macro- and micronutrients, usually proportionally to the olive mill wastewater dose. Cadmium and Pb were within the permissible limits. The increased OMW had different behaviour on the soil nutritional balances of different elements, leading to nutrient imbalances, although in some cases, they were improved. However, the plant growth was not affected, and it was improved under 10 L m-2 and 15 L m-2 doses. The results offer valuable data about the use of OMW as organic fertilizer for crops and their potential impact on soil properties.

Preparation, Characterization, and Environmental Safety Assessment of Dithiocarbazate Loaded Mesoporous Silica Nanoparticles.

Dithiocarbazates comprise an important class of Schiff bases with remarkable biological applications due to the imine group present in their structure. However, full exploitation of the biological activity of 3-methyl-5-phenyl-pyrazoline-1-(S-benzyldithiocarbazate) (DTC) is limited due to its easy degradation and poor solubility in aqueous solutions. The loading of DTC into mesoporous silica nanoparticles (MSiNPs) can be an excellent strategy to improve the solubility of DTC in the aqueous medium. Therefore, the main goal of the present work was to design MSiNP-DTC and to evaluate the success of the loading process by measuring its physicochemical properties and evaluating the environmental safety of the new DTC formulation using different aquatic organisms, such as the microalgae Raphidocelis subcapitata, the macrophyte Lemna minor, and the marine bacterium Aliivibrio fischeri. DTC, MSiNP, and MSiNP-DTC concentrations ranging from 8.8 to 150 mg L-1 were tested for all the species, showing low toxicity against aquatic organisms. Loading DTC into MSiNPs caused a slight increase in the toxicity at the concentrations tested, only allowing for the estimation of the effect concentration causing a 20% reduction in bioluminescence or growth rate (EC20). Therefore, despite the potential of MSiNPs as a drug delivery system (DDS), it is of utmost importance to assess its impact on the safety of the new formulations.

Application of a standard risk assessment scheme to a North Africa contaminated site (Sfax, Tunisia) -Tier 1.

Phosphorus is a critical element to agriculture, consequently global phosphate rock demand will remain rising to feed a growing world population. The beneficiation of phosphorous ore gives rise to several tons of a waste by-product [phosphogypsum (PG)] which valorisation is limited, within other reasons, by the risks posed to environment and human health. Although threatening, the accumulation in stacks is the only procedure so far practiced by several countries as a means to get rid of this industrial externality. As part of a NATO Science for Peace Project (SfP 983311) this study describes the application of an environmental risk assessment (ERA) framework, to assess the risks posed by a PG stack to the surrounding soils, in Sfax, Republic of Tunisia. The ERA followed a weight of evidence approach, supported by two lines of evidence (LoE): the chemical (ChemLoE) and the ecotoxicological (EcotoxLoE). Integrated risks point for risk values greater than 0.5 in soils collected in PG stack surrounding area. Soil salinization, has likely contributed to the exacerbation of risks, as well as to the lack of consistency between both LoEs. This study highlights the need of rethinking the weight given to each LoE in ERA, in areas where soil salinization is a reality.

Health risk assessment of heavy metals exposure via consumption of crops grown in phosphogypsum-contaminated soils.

The management of phosphogypsum (PG) heap, located south of the Sfax city in Tunisia, has been going on for decades. But dumping this solid waste still poses environmental problems. Even though valorized as amendment to agriculture soils, the sanitary impact of this practice is not seriously considered. To assess the risk of the transference of contaminants from PG to agricultural soil-plants food chain, a wild plant species Salicornia arabica grown in PG-contaminated field and tomato (Lycopersicon esculentum) and oat (Avena sativa) grown in laboratory using different rates (10, 20 and 30%) of PG amendment, were tested. The cadmium, lead, chromium, nickel, copper and zinc concentrations in soils and plants were determined by atomic absorption spectrometry and by inductively coupled plasma-mass spectrometry, respectively. Measurements showed that Ni, Cu and Pb levels in the amended soils were below international standards except for Cd and Cr which exceeded Chinese, FAO/WHO and European allowable standard limits. Gathered results showed that the more the PG rate increases, the more the bioconcentration factors of heavy metals increased in plants, particularly in the roots. This is a prospective study assuming direct or indirect exposure scenario of different human cohorts by consuming varied common food stuffs. The Human Exposure to Soil Pollutants evaluation and United State Environment Protection Agency models were adopted for the hazard quotient calculation to assess the acceptability of sanitary risk related to each metal. The direct and indirect health risk assessments varied in the decreasing order: children, adolescents and then adults. Therefore, the PG amendment must not exceed the rate of 10%.

Ecotoxicity of titanium silicon oxide (TiSiO4) nanomaterial for terrestrial plants and soil invertebrate species.

The huge evolution of nanotechnology and the commercialization of nanomaterials (NMs) positively contributed for innovation in several industrial sectors. Facing this rapid development and the emergence of NMs in the market, the release of this nanometric sized materials in the environment and the possible impact on different ecosystem components attracted the attention of researchers in the last few years. In our study we aimed to assess the impact of titanium silicon oxide nanomaterial (nano-TiSiO4) on soil biota to estimate a risk limit for this material. In the present research a battery of standardized ecotoxicological assays aimed at evaluating a wide range of endpoints (avoidance and reproduction of earthworms and collembolans, emergence/growth of four selected terrestrial plants) were carried out, using OECD artificial soil as test substrate spiked with aqueous suspension of different concentrations of nano-TiSiO4. The results showed a maximum avoidance percentage of 40% for earthworms (Esenia andrei) at the highest concentration tested (1000mgkg(-1) soildw of nano-TiSiO4). No significant effect on the reproductive function of both invertebrate species was recorded. Nevertheless, significant phytotoxic data was registered at least for the growth of dicotyledonous plant species (Lactuca sativa and Lycopersicon lycopersicum) with EC20 values ranging between 236 and 414 mg kg(-1) soildw of nano-TiSiO4 for L. sativa dry mass and fresh mass, respectively. Further, the characterization of nano-TiSiO4 in suspensions used to spike the soil, performed by Dynamic Light Scattering, showed the formation of aggregates with important average size diameter, thus demonstrating that the toxic effects observed were likely not size dependent. A deterministic PNEC (predicted no effect concentration) for this NM of 10.02mg kg(-1) soildw of nano-TiSiO4, is suggested, while no more ecotoxicological information exists.

Phosphogypsum as a soil fertilizer: Ecotoxicity of amended soil and elutriates to bacteria, invertebrates, algae and plants.

Phosphogypsum (PG) is a metal and radionuclide rich-waste produced by the phosphate ore industry, which has been used as soil fertilizer in many parts of the world for several decades. The positive effects of PG in ameliorating some soil properties and increasing crop yields are well documented. More recently concerns are emerging related with the increase of metal/radionuclide residues on soils and crops. However, few studies have focused on the impact of PG applications on soil biota, as well as the contribution to soils with elements in mobile fractions of PG which may affect freshwater species as well. In this context the main aim of this study was to assess the ecotoxicity of soils amended with different percentages of Tunisian phosphogypsum (0.0, 4.9, 7.4, 11.1, 16.6 and 25%) and of elutriates obtained from PG - amended soil (0.0, 6.25, 12.5 and 25% of PG) to a battery of terrestrial (Eisenia andrei, Enchytraeus crypticus, Folsomia candida, Hypoaspis aculeifer, Zea mays, Lactuca sativa) and aquatic species (Vibrio fischeri, Daphnia magna, Raphidocelis subcapitata, Lemna minor). Both for amended soils and elutriates, invertebrates (especially D. magna and E. andrei) were the most sensitive species, displaying acute (immobilization) and chronic (reproduction inhibition) effects, respectively. Despite the presence of some concerning metals in PG and elutriates (e.g., zinc and cadmium), the extremely high levels of calcium found in both test mediums, suggest that this element was the mainly responsible for the ecotoxicological effects observed. Terrestrial and aquatic plants were the most tolerant species, which is in line with studies supporting the application of PG to increase crop yields. Nevertheless, no stimulatory effects on growth were observed for any of the species tested despite the high levels of phosphorus added to soils by PG. Given the importance of soil invertebrates for several soil functions and services, this study gives rise to new serious concerns about the consequences of PG applications on agricultural soils.