Iron mineralogy as a fingerprint of former steelmaking activities in river sediments.

Submerged sediment cores were collected upstream of a dam in the Orne River, northeastern France. This dam was built in the context of steelmaking to constitute a water reservoir for blast furnace cooling and wet cleaning of furnace smokes. The dam also enhanced sediment deposition in the upstream zone. This study was performed to unravel the contamination status of sediments and to evidence possible contribution sources. The sediment layers were analyzed for water content, grain size, chemical composition, crystalline phases at a bulk scale and poorly crystalline and amorphous phases at a sub-micrometer scale. Visual aspect, texture, color, and chemical and mineralogical analyses showed that the settled sediments were mainly composed of fine black matter, certainly comprising steelmaking by-products. Those materials were highly enriched with Fe, Zn, Pb and other trace metals, except for a relatively thin layer of surficial sediments that had settled more recently. Bulk mineralogy revealed crystalline iron minerals, such as magnetite, goethite, wuestite and pyrite, in the deep layers of the sediment cores. Furthermore, microscopic investigations evidenced the presence of ferrospheres, goethite nanoparticles and newly formed Fe-aluminosilicates; all originating from the former steelmaking facilities. The variation of iron mineralogy, combined with specific chemical profiles and other sediment features, demonstrate the different contributions that constitute the sediment deposit. Furthermore, chemical and mineralogical features of goethite and Fe-aluminosilicates could be used as a fingerprint for such contaminated sediments.

Hydrodynamic influence on reservoir sustainability in semi-arid climate: A physicochemical and environmental isotopic study.

Water scarcity and increasing water demand require the development of water management plans such as establishing artificial lakes and dams. Plans to meet water needs are faced by uprising challenges to improve water quality and to ensure the sustainability of hydro-projects. Environmental isotopes coupled to water physicochemical characteristics were investigated over a biennial cycle to assess both geomorphological and environmental impacts on the water quality of a reservoir situated in an intensively used agricultural watershed under a Mediterranean semi-arid climate. The particularity of the semi-arid climate and the diverse topography generate a continental and orographic rain effect on the isotopic composition of precipitation and the water recharged sources. The studied reservoir responds quickly to land-use activities and climatic changes as reflected by temporal and spatial variations of water chemistry and isotopic composition. Increasing changes in precipitation rate and dry periods significantly modified the water isotopic composition in the reservoir. During the first year, hydrogen (δD) and oxygen (δ18O) isotopes are depleted by 6 and 2‰ between dry and wet season, respectively. While a shift of -2‰ for δD and -1‰ for δ18O was detected during the second annual cycle. Environmental isotopic compositions demonstrate for the first time the occurrence of groundwater inflow to the central (Cz) and dam (Dz) zones of the Qaraaoun reservoir. The Cz and Dz can be considered as open water bodies subjected to dilution by groundwater inflow, which induces vertical mixing and reverse isotopic stratification of the water column. In the contrary, the river mouth zone acts as a closed system without groundwater intrusion, where heavy water accumulates and may act as a sink for contaminants during dry season. Groundwater influx acts as a dilution factor that renews the hypolimnion, and minimizes the perturbations induced by both internal biogeochemical reactions and external hydrological variations. Attention should be devoted to the hydrogeological location of planned reservoirs, which should take into account the vicinity of shallow water table to insure good water quality and water sustainability.

Role of phosphogypsum and NPK amendments on the retention or leaching of metals in different soils.

Column leaching tests were conducted to investigate the effects of soil physicochemical characteristics on metal mobility in the subsurface. The metals investigated originated from disposed industrial waste byproducts and from agrochemicals spread over the farmlands. Soil column tests can provide insights into leaching of metals to underlying water compartments. The findings of this study can be used for prevention strategies and for setting risk assessment approaches to land-use and management, and soil and water quality and sustainability. Soils collected from an industrial (IS) watershed and an agricultural (AQ) hydrographic basin were used in soil column leaching experiments. The soil samples were characterized for mineralogy, functional groups, grain size, surface charge, soil type, porosity, and cation exchange capacity (CEC) along with elemental composition. Varying concentrations of phosphogypsum industrial waste or agrochemical (NPK fertilizer) was then added to the surface of the packed columns (n = 28). The columns were subjected to artificial rain over a period of 65 days. Leachates were collected and analyzed for dissolved Na(+), K(+), and Cd(2+) throughout the experimental period, whereas residual Cd content in the subsurface soil was measured at the end of the experiment. Physicochemical characterization indicated that the AQ soil has a higher potential for metal retention due to its fine clay texture, calcareous pH, high organic matter content and CEC. Metal release was more prominent in the IS soil indicating potential contamination of the surrounding soil and water compartments. The higher metal release is attributed to soil physicochemical characteristics. High calcium concentrations of phosphogypsum origin is expected to compete for adsorbed bivalent elements, such as Cd, resulting in their release. The physicochemical characteristics of the receiving media should be taken into consideration when planning land-use in order to achieve sustainable development. Soil physiochemical characteristics play a key role in determining the behavior and fate of elements upon application of amendments. Sandy soils should not be assigned to industrial zones or landfills due to their high permeability, unlike fine clay soils. Furthermore, application of fertilizers on sandy soils can threaten groundwater quality, whereas their extensive use on clayey soil can cause soil salinisation.

Reservoir sediments: a sink or source of chemicals at the surface water-groundwater interface.

This study delineates the physical, chemical, and biological effects resulting from anthropogenic and endogenic activities in a sensitive dammed reservoir situated in a semi-arid region. The reservoir is characterized by two major flow regimes: a wet fill hydrologic regime and a dry spill one. A seasonal sampling campaign was carried out over a period of 2 years (2011-2013) where water samples were collected across the water column and from piezometers just outside the perimeter of the reservoir. Similarly, sediments were collected from the corresponding areas beneath the water column. The water samples were analyzed for environmental isotopic ratios, elemental composition, and physical, biological and chemical parameters, whereas the sediment and algal samples were subjected to physical, mineralogical, spectroscopic, and microscopic analyses. This investigation indicated that the dam had resulted in the alteration of the biogeochemical cycle of nutrients as well as the degradation of the sediment and water quality. The hydrological and biogeochemical processes were found to induce vertical downward transport of chemicals towards the fine grained calcareous sediments during the fill mode, whereas the sediments acted as a source of a chemical flux upward through the water column and downward towards the groundwater during the spill mode. The geomorphological characteristics of the reservoir enhanced the strong hydrological connectivity between the surface water and the groundwater where the reservoir responded quickly to natural and anthropogenic changes in the upper watershed. The water and sediments in the sensitive spill mode were of poor quality and should receive more attention due to the potential hazard for the associated hydro-project and the sustainability of the agricultural soil in the long term. Thus, a safe water and sediment management plan should be implemented in order to improve the dam functionality and to safeguard the precious water resources.

Metal binding in soil cores and sediments in the vicinity of a dammed agricultural and industrial watershed.

The environment is witnessing a downgrade caused by the amelioration of the industrial and agricultural sectors, namely, soil and sediment compartments. For those reasons, a comparative study was done between soil cores and sediments taken from two locations in the Qaraaoun reservoir, Lebanon. The soil cores were partitioned into several layers. Each layer was analyzed for several physicochemical parameters, such as functional groups, particle size distribution, ζ-potential, texture, pH, electric conductivity, total dissolved solids, organic matter, cation exchange capacity, active and total calcareous, available sodium and potassium, and metal content (cadmium, copper, and lead). The metal content of each site was linked to soil composition and characteristics. The two sites showed distinguishable characteristics for features such as organic matter, pH, mineral fraction, calcareous, and metal content. The samples taken toward the south site (Q1), though contain lower organic matter than the other but are more calcareous, showed higher metal content in comparison to the other site (Q2) (average metal content of Q1 > Q2; for Cd 3.8 > 1.8 mg/kg, Cu 28.6 > 21.9 mg/kg, Pb 26.7 > 19 mg/kg). However, the metal content in this study did not correlate as much to the organic matter; rather, it was influenced by the location of the samples with respect to the dam, the reservoir's hydrodynamics, the calcareous nature of the soil, and the variation of the industrial and agricultural influence on each site.

Applying physicochemical approaches to control phosphogypsum heavy metal releases in aquatic environment.

One of the most important sources of solid waste in the Mediterranean Basin ecosystem originated from the phosphate fertilizer industries, which discharge phosphogypsum (PG) directly into aquatic environments or are stacked on stockpiles. The present study investigates metal release from PG under the influence of variable pH, increasing PG mass content, and complexing organic matter ligands. Major ions from PG leachates, grain size and charge, main functional groups along with metal leachability (Pb, Cd, Cr, Cu, and Zn) were determined using ion chromatography, laser diffraction, zetameter, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy, respectively. The complete dissolution of PG recorded is at 2 g/L. Saturation and supersaturation with respect to PG may occur at concentrations of 3 and 4 g/L, respectively, revealing a clustering phenomenon leading to heavy metal encapsulation within the aggregates. Organic ligands such as citrate may trigger the cationic exchange within the PG suspension leading to ion release. As these factors are considered as specific process involving the release of contaminants from PG during storage under natural conditions, this study could set the foundations for PG remediation in aquatic environment. Organic ligands under controlled pH conditions could be utilized in treating fertilizer industrial wastes by taking into consideration the particularity of the receiving area, thus decreasing metal hazardous impact on natural media.