Chromium Removal Using Soil Loaded with Green Iron Nanoparticles.

Chromate is considered as a serious environmental problem due its toxicity. Iron nanoparticles produced by green tea polyphenols (GT-nZVI) is a powerful reductant, which can effectively reduce Cr(VI) to Cr(III). Nano ZVI suspension was initially conceived ideal for direct injection in the contaminated aquifers. However GT-nZVI presents limited mobility in calcareous aquifers. For this reason the incorporation of nanoiron in a permeable reactive barrier was investigated as an alternative mode of GT-nZVI application. Namely an amount of soil was loaded with nZVI (0.40 mmol/g of soil) and was evaluated for Cr(VI) removal by conducting batch and column tests. Batch tests were carried out by mixing soil samples, loaded with different levels of nZVI from 0.04 to 0.40 mmol per gram, with contaminated groundwater (GW) containing 1300 ppb Cr(VI). Cr(VI) concentration dropped below detection limit within 1 day using the highest nZVI dose. Soil pre-loaded with nZVI (S-nZVI) presented also high efficiency for chromates remediation, when tested under flow conditions by conducting column tests.

A DPSIR Approach to Selected Cr(VI) Impacted Groundwater Bodies of Central Greece.

The holistic approach of Driver-Pressure-State-Impact-Response (DPSIR) methodology was applied to selected Cr(VI) impacted groundwater bodies of Central Greece. The main driving forces in the study areas are agricultural activities, urban and industrial development as well as tourism. The main pressures induced by the anthropogenic activities are fertilizer use, uncontrolled urban sewage disposal and industrial effluents discharges. Groundwater stress is caused by the qualitative degradation due to Cr(VI), NO3-, Cl- and SO42- contamination. Hexavalent chromium occurrence is attributed to both geogenic and anthropogenic sources. The maximum Cr(VI) concentration (11.7 mg/L) was measured in Oinofyta area. Important impacts are the deterioration of groundwater body chemical status as well as the decline of groundwater use efficiency. Based on the applied DPSIR, a management framework is proposed in order to address the complex environmental issue of Cr(VI) in the study areas.

The Origin of Hexavalent Chromium as a Critical Parameter for Remediation of Contaminated Aquifers.

Two different cases of Cr(VI) contaminated ophiolitic aquifers are presented herein. The first is located at Vergina (Northern Greece), where the maximum Cr(VI) concentration measured was 64 µg/L, being one of the highest geogenic concentrations recorded globally in areas with similar geological background. The second case is located at Inofyta (Central Greece), a makeshift industrial area, where the maximum detected Cr(VI) concentration exceeds 10,000 µg/L, indicating clearly anthropogenic activities as the main source. Although for the Vergina aquifer, area-wide institutional measures and in some cases pump and treat systems might be sufficient to ensure a safe water supply for domestic and agricultural use, this is not the case for the contaminated aquifer of Inofyta. There a comprehensive remediation scheme should be properly implemented adopting, however, realistic remediation targets, that should also take into account the geogenic contribution to the high Cr(VI) groundwater concentrations measured.

The role of activated carbon and disinfection on the removal of endocrine disrupting chemicals and non-steroidal anti-inflammatory drugs from wastewater.

Endocrine disrupting chemicals and non-steroidal anti-inflammatory drugs are two important groups of emerging pollutants due to their toxicological and chemical characteristics and their persistent detection in the aquatic environment. Wastewater treatment plants are a significant pathway for their transfer to the water courses. It is well evidenced that these chemicals are only partially removed through biological treatment of wastewater and therefore being detected in secondary effluents. This work focuses on the evaluation of the efficiency of two well-established disinfection technologies (chlorination and UV irradiation) along with UV/H2O2 and powdered activated carbon (PAC) to remove these chemicals from biologically treated wastewater. Based on the results it is shown that appreciable removal efficiencies due to chlorination should be expected for most of the target compounds, whereas this was not the case for ibuprofen and ketoprofen. With the exemption of diclofenac and ketoprofen direct UV irradiation did not efficiently removed target compounds for UV doses usually applied for disinfection purposes. The application of advanced UV treatment through the addition of H2O2 although resulted in increased removal of the target compounds is not sufficient at moderate UV and H2O2 doses to achieve satisfactory removal efficiencies. PAC use resulted in sufficient removal of target compounds although high PAC doses were required for some chemicals. Comparison of Freundlich isotherms of this study with those of other studies, derived employing water samples, suggested that the water matrix along with the target compounds concentration range can significantly affect the outcome of the experiments.

Multi wall carbon nanotubes application for treatment of Cr(VI)-contaminated groundwater; Modeling of batch & column experiments.

Multi wall carbon nanotubes (MWCNTs) are carbonaceous nanomaterials with novel adsorption properties. In this study MWCNTs were used as adsorbents for hexavalent chromium, Cr(VI), and the influence of operating parameters, on adsorption process, such as pH, MWCNTs and Cr(VI) concentration, and contact time have been investigated. Batch and column experiments were carried out in order to investigate the removal efficiency of MWCNTs for different Cr(VI) concentrations related to groundwater polluted by either anthropogenic activities or by geogenic processes. The experimental results showed that pH was the most crucial factor for adsorption efficiency. Cr(VI) adsorption was inversely proportional with pH value and more specifically adsorption was significantly decreased for pH values higher than 7. The effect of adsorbent's concentration showed the high adsorption capacity of MWCNTs. The adsorption process was very fast since was almost completed within 1 h. Different isotherm models have been adopted to interpret the experimental equilibrium data, as well as two mass-transfer based model were used to describe the dynamic behavior of Cr(VI) sorption phenomenon in column experiments.

Nanomaterials application for heavy metals recovery from polluted water: The combination of nano zero-valent iron and carbon nanotubes. Competitive adsorption non-linear modeling.

Carbon Nanotubes (CNTs) and nano Zero-Valent Iron (nZVI) particles, as well as two nanocomposites based on these novel nanomaterials, were employed as nano-adsorbents for the removal of hexavalent chromium, selenium and cobalt, from aqueous solutions. Nanomaterials characterization included the determination of their point of zero charge and particle size distribution. CNTs were further analyzed using scanning electron microscopy, thermogravimetric analysis and Raman spectroscopy to determine their morphology and structural properties. Batch experiments were carried out to investigate the removal efficiency and the possible competitive interactions among metal ions. Adsorption was found to be the main removal mechanism, except for Cr(VI) treatment by nZVI, where reduction was the predominant mechanism. The removal efficiency was estimated in decreasing order as CNTs-nZVI > nZVI > CNTs > CNTs-nZVI* independently upon the tested heavy metal. In the case of competitive adsorption, Cr(VI) exhibited the highest affinity for every adsorbent. The preferable Cr(VI) removal was also observed using binary systems of the tested metals by means of the CNTs-nZVI nanocomposite. Single species adsorption was better described by the non-linear Sips model, whilst competitive adsorption followed the modified Langmuir model. The CNTs-nZVI nanocomposite was tested for its reusability, and showed high adsorption efficiency (the qmax values decreased less than 50% with respect to the first use) even after three cycles of use.

Investigation of hexavalent chromium sorption in serpentine sediments.

In this study the removal of hexavalent chromium (Cr6+) by serpentine sediments was investigated in order to delineate Cr6+ sorption behavior in aquifers with ultramafic geologic background. Batch experiments were conducted in order to determine the influence of several parameters on Cr6+ removal, including the pH of the sediment solution, mineralogy, sediment's particle size and Cr6+ initial concentration. The results showed that Cr6+ removal was due to both adsorption and reduction phenomena. Reduction was attributed to the presence of a magnetic fraction in the sediment, mostly related to magnetite, which contributed almost 50% of the total removal in the pH range 3-7. Adsorption behavior was dominated by the finer sediment fraction (d<0.075mm). The amount of Cr6+ adsorbed was constant in the pH range 3-7, while it decreased sharply in the range 7-8.5. Cr6+ adsorption was found to increase and decrease proportionally with increasing initial Cr6+ concentration of and particle size, respectively. The linear Langmuir and Freundlich adsorption isotherms were used to describe the experimental data, with Freundlich providing a better fit to determine distribution factors for transport modeling.

Origin and concentration profile of chromium in a Greek aquifer.

In this paper the origin and concentration of chromium (Cr) in an ophiolitic aquifer in Vergina, northern Greece were investigated. The study area has only agricultural activity so that industrial Cr contamination was precluded. Soil sampling included topsoil and drillcore samples collected down to 98 m depth. Groundwater samples were collected from three existing wells and a spring at the area and from different depths of the soil boring using the discrete sampling method. Mineralogical analysis of soils confirmed the presence of ultramafic minerals, including chrysotile and chromite. Soil elemental analysis showed significant concentration of total chromium (Crtot; max 12,000 mg/kg) and hexavalent chromium (Cr(VI); max 7.5mg/kg). Significant Crtot (91 µg/L) and Cr(VI) (64 µg/L) concentrations exceeding the drinking water limit of 50 µg/L were also detected in groundwater. In both the discrete soil and groundwater samples a decreasing trend of Cr(VI) concentration was observed with increasing depth, while Crtot increased. The increasing trend in Crtot is attributed to the increasing contribution of unweathered ultramafic minerals with depth, while the decreasing Cr(VI) may be related to the increasing soil pH that does not favor Cr(III) oxidation by Mn-oxides.