In this study, two carbon materials [chicken manure biochar (CMB) and black carbon (BC)] were investigated for their effects on the reduction of hexavalent chromium [Cr(VI)] in two spiked [600 mg Cr(VI) kg⁻¹] and one tannery waste contaminated [454 mg Cr(VI) kg⁻¹] soils. In spiked soils, both the rate and the maximum extent of reduction of Cr(VI) to trivalent Cr [Cr(III)] were higher in the sandy loam than clay soil, which is attributed to the difference in the extent of Cr(VI) adsorption between the soils. The highest rate of Cr(VI) reduction was observed in BC-amended sandy loam soil, where it reduced 452 mg kg⁻¹ of Cr(VI), followed by clay soil (427 mg kg⁻¹) and tannery soil (345 mg kg⁻¹). X-ray photoelectron microscopy confirmed the presence of both Cr(VI) and Cr(III) species in BC within 24 h of addition of Cr(VI), which proved its high reduction capacity. The resultant Cr(III) species either adsorbs or precipitates in BC and CMB. The addition of carbon materials to the tannery soil was also effective in decreasing the phytotoxicity of Cr(VI) in mustard (Brassica juncea L.) plants. Therefore, it is concluded that the addition of carbon materials enhanced the reduction of Cr(VI) and the subsequent immobilization of Cr(III) in soils.

Electric arc furnace (EAF) dust and slag, materials which contain high metals in their composition, were improperly disposed in an industrial steel mill site between 1963 and 1999. Previous environmental investigations identified anomalous concentrations of metals in local groundwater but failed to relate these abnormalities to the disposed material or to natural geochemical processes. Aiming to identify the origin of such abnormalities, exploratory and spatial data analysis (EDA-SDA) method was applied on a hydrogeochemical data set obtained through 5 sampling campaigns in 32 groundwater monitoring wells installed upstream and downstream of the area impacted by the steel mill activities. Boxplot class-based and Eh vs. pH maps of physicochemical log-transformed data identified that wells located under the influence of EAF slag deposits in topographic hollows had lower Eh potential and increased electrical conductivity and pH, when compared to wells in the topographical nose of the surveyed area. Metal distribution maps showed that Al, Ca, K, Mg, Na, and Sr were consistently higher in topographic hollows while concentrations of Co, Cu, Cr, and Li were higher near the former steel-making plant, located in the topographical nose. Ba, Fe, Mn, and Zn, important indicators of EAF slag and dust, were observed in both topographic settings. Variable clustering was able to capture the relations among metals and thus validate the log-normalized data structure to be used into wells clustering. Clustering through the mclust algorithm carried out for two and three clusters allowed the distinction among localities that received an input of metals from dust or slag and those not influenced by either residue. This paper demonstrates that EDA-SDA is an effective method to identify areas under the influence of contamination from industrial activities from areas not affected by anthropogenic contamination.

This paper presents the efficacy of zero-valent iron nanoparticles (ZVINs), magnetic iron oxide nanoparticles (MINs), zero-valent iron nanoparticles/sugarcane bagasse (ZVIN-SB) composite and magnetic iron oxide nanoparticles/sugarcane bagasse (MIN-SB) composite in immobilizing chromium present in tannery sludge. The optimized values for the immobilization of chromium by the adsorbents were found to be 48 h, 100 g/kg and 7, respectively, for time, adsorbent dosage and pH. The maximum uptake capacity was found to be 429.75, 539.25, 587.25 and 625.8 mg/kg, respectively, for ZVIN, MIN, ZVIN-SB and MIN-SB. The desorption study of the unamended sludge and sludge amended by ZVIN, MIN, ZVIN-SB and MIN-SB was carried out with three different desorbing media (0.1 N HCL, DIW and 0.1 N NaOH). It was found that the cumulative concentration of leachate chromium was more in basic condition than in neutral and acidic conditions. In column studies, the concentration of leachate chromium attained 0 mg/L at 24, 15, 18 and 14 pore volumes, respectively, for the sludge amended by ZVIN, MIN, ZVIN-SB and MIN-SB. The experimental adsorption data fitted well with pseudo-first-order kinetics. The zero-order kinetics accurately predicted the experimental desorption capacity (q ₑ) of the sludge amended by ZVIN, MIN, ZVIN-SB and MIN-SB. The Fourier transform infrared spectroscopy (FTIR) analysis showed that the amine, carboxyl, iron compounds, etc. present in the adsorbents were the chief causes for the immobilization of chromium. The X-ray diffraction (XRD) analysis of the sludge showed the presence of trivalent chromium compounds at a higher concentration.

Polycyclic aromatic hydrocarbons (PAHs) and heavy metals are the two most important groups of pollutants associated with rail transport. Both have a serious negative impact on the natural environment, including human health and degradation of sensitive ecosystems. In our study, apart from qualitative and quantitative analysis of the main PAHs and heavy metals associated with rail, we tried to assess composition of specific compounds related to functional areas of railway infrastructure and to distinguish potential chemical markers which can be used for identification of pollution. Moreover, we evaluated the applicability of plants overgrowing railway infrastructure as bioindicators of rail-associated pollution. Though we confirmed that high amounts of PAHs and heavy metals in soil are characteristic for intensively used railway infrastructure, we found no typical pollution profiles for the differently used areas (i.e. platforms, sidings, cleaning bays). The major source of these contaminants is petroleum products used in conservation of railway infrastructure and rolling stock. As far as the use of plants overgrowing railway infrastructure as bioindicators of rail-associated pollution is concerned, it is rather limited, due to frequent application of herbicides for security and track stability reasons.

This paper proposes an extraction procedure for the speciation analysis of inorganic antimony in sediment samples using slurry sampling and hydride generation atomic absorption spectrometry. The optimization step of extraction of the species was performed employing a full two-level factorial design (2³) and a Box-Behnken matrix where the studied factors in both experiments were: extraction temperature, ultrasonic radiation time, and hydrochloric acid concentration. Using the optimized conditions, antimony species can be extracted in closed system using a 6.0 M hydrochloric acid solution at temperature of 70 °C and an ultrasonic radiation time of 20 min. The determination of antimony is performed in presence of 2.0 M hydrochloric acid solution using HG AAS by external calibration technique with limits of detection and quantification of 5.6 and 19.0 ng L⁻¹ and a precision expressed as relative standard deviation of 5.6 % for an antimony solution with concentration of 6.0 μg L⁻¹. The accuracy of the method was confirmed by analysis of two certified reference materials of sediments. For a sample mass of sediment of 0.20 g, the limits of detection and quantification obtained were 0.70 and 2.34 ng g⁻¹, respectively. During speciation analysis, antimony(III) is determined in presence of citrate, while total antimony is quantified after reduction of antimony(V) to antimony(III) using potassium iodide and ascorbic acid. The method was applied for analysis of six sediment samples collected in São Paulo Estuary (Bahia State, Brazil). The antimony contents obtained varied from 45.3 to 89.1 ng g⁻¹ for total antimony and of 17.7 to 31.4 ng g⁻¹ for antimony(III). These values are agreeing with other data reported by the literature for this element in uncontaminated sediment samples.

The feasibility of date seeds as a new low-cost natural adsorbent for the removal of dissolved organic carbon (DOC) from oily produced water was investigated. The aim of this study was to elucidate the mechanism associated with the removal of DOC and to find the best equilibrium isotherms and kinetic models for DOC removal in batch adsorption experiments. The effect of various physicochemical parameters such as initial DOC concentration (18.5–93.5 mg/L), solution pH (4–9), temperature (25–45 °C), and date seeds dosages (0.5–2.0 g) was evaluated. The equilibrium stage was attained after a contact time of 120 min. The maximum DOC removal was 82 % for 93.5 mg/L of DOC concentration. The equilibrium data were well represented by the Langmuir isotherm. The maximum monolayer adsorption capacity of date seeds was found to be 74.62 mg/g. The separation factor, R L, from the Langmuir equation and the Freundlich constant, n, indicated a favorable adsorption. The kinetic studies indicated that the adsorption process follows the pseudo-second-order kinetics. The adsorption of DOC is governed by both surface and pore diffusion. The results revealed that the DOC uptake decreases when temperature and pH increases. The adsorption process has been found exothermic in nature, and the thermodynamic parameters were determined. The Langmuir isotherm model equation was adopted to design a single-stage batch absorber for DOC adsorption onto date seeds. The study demonstrated that date seeds can be considered as a promising low-cost adsorbent for the removal of DOC from oily produced water.

The effluent of the ornamental rock industry is characterized by presenting great concentrations of total solids, high contents of iron, and elevated pH, all responsible for the contamination of the superficial and ground waters, destruction of the soil, the vegetation, and the silting of the rivers. The purpose of this study is to assess the cytotoxic and genotoxic effects and the anatomical changes caused by the effluents arising from the ornamental rock polishing industry in root apex cells of Allium cepa L. (Amaryllidaceae). The samples of the effluent were collected in a polishing industry located in Nova Venécia, State of Espírito Santo, and were analyzed by mass spectrometry and atomic emission. Bulbs of A. cepa were exposed to the effluent at 12.5, 25, 37.5, 50, 75, and 100 % concentrations (residue in raw form) (v/v) for a period of 20 days. For the positive control, metilmethanesulfonate (MMS) at 4 × 10⁻⁴-M concentration was used, and distilled water was used for the negative control. The experiment was assessed taking into consideration the following parameters: mitotic index, frequency of chromosomal and nuclear abnormalities in the root apical meristem, and root anatomy. The mitotic index suffered a decrease proportional to the increase in the concentration of effluent. All the concentrations of the effluent led to chromosomal and nuclear abnormalities being stickiness and nuclear shoots the most frequent. The root apex evidenced changes that reflected on the decrease of the percentage area of the protoderm and the fundamental meristem and the increase in the areas of the cap and quiescent center. The symptoms of toxicity are related to the high frequency of cell in cellular death process observed in the roots exposed to the higher concentrations and to the decrease in the mitotic index of the apical root meristem.

The study investigated phosphate adsorption from aqueous solutions using chemical- and thermal-modified bentonite in batch system. The adsorbent was characterized by SEM, BET, and FTIR spectroscopy. Contact time, beginning phosphate concentration, pH of the solution, and the effects of the temperature on phosphate adsorption capacity were determined by a series of experimental studies. In a wide pH range (3–10), high phosphate removal yields were obtained (between 94.23 and 92.26 %), and with the increase in temperature (from 25 to 45 °C), phosphate removal increased. Langmuir and Freundlich isotherms were used to determine the sorption equilibrium, and the results demonstrated that equilibrium data displayed better adjustment to Langmuir isotherm than the Freundlich isotherm. Phosphate sorption capacity, calculated using Langmuir equation, is 20.37 mg g⁻¹ at 45 °C temperature and pH 3. Mass transfer and kinetic models were applied to empirical findings to determine the mechanism of adsorption and the potential steps that control the reaction rate. Both external mass transfer and intra-particle diffusion played a significant role on the adsorption mechanism of phosphate, and adsorption kinetics followed the pseudo-second-order-type kinetic. Furthermore, thermodynamic parameters (ΔH°, ΔG°, ΔS°) which reveal that phosphate adsorption occur spontaneously and in endothermic nature were determined. The results of this study support that bentonite, which is found abundant in nature and modified as an inexpensive and effective adsorbent, could be used for phosphate removal from aqueous solutions.

Solanum nigrum L., a potential cadmium (Cd) hyper-accumulator, has not currently been investigated to identify if it has a strong simultaneous accumulative ability to Cd, copper (Cu), zinc (Zn), or lead (Pb) in contaminated soils. In this study, a pot culture experiment was conducted to investigate the phytoremediation effects of S. nigrum L. on these heavy metals. The potential hyper-accumulative characteristics of S. nigrum L. were also discussed. The results showed that S. nigrum L. remediation effects were not inhibited by multi-heavy metals in contaminated soil. On the contrary, the height and wet and dry weights of S. nigrum L. increased compared to the control treatments and to treatments using only one heavy metal contaminant. Results from the Cd treatment experiments showed 1.66- and 1.45-fold increases in stem and root levels; there were also 1.24-, 2.17-, and 1.61-fold extraction increases in the leaves, stems, and roots, respectively. The differences found in shoot and root bioaccumulation coefficient (BC) factors for multi-heavy metal (MHM) treatment were higher than for a single Cd treatment. These results indicate that S. nigrum L. could stimulate biomass production and that it has a strong ability to tolerate and accumulate Cd in contaminated soils with Pb, Zn, and Cu. This study shows that the remediation scope for S. nigrum L. is greater than currently believed and that it will also remove Pb, Zn, and Cu while extracting Cd from contaminated soils.

Inadequately treated effluents from industry have serious environmental and public health concerns. Even low level discharges create problems through accumulation in water and soil. In the present work, the pollutant accumulating capacity and the general environmental health status of soil which is a repository of treated and untreated effluent discharges and solid waste dumping of a giant pulp and paper mill have been evaluated with respect to some selected physicochemical parameters. The pollutant accumulating capacity of the soil in seven well-defined sites in and around the mill was found with reference to a “control” site with no history of receiving effluent discharges or solid wastes. The changes in texture, bulk density, water-holding capacity, electrical conductivity, pH, organic carbon, cation exchange capacity, exchangeable sodium, etc. of the soil up to the normal tilled depth were observed in different seasons. In most sites, the soil organic carbon was poorly correlated to the bulk density, water-holding capacity, pH, and clay and sand contents, indicating an unhealthy state of the soil and, correspondingly, nearly exhausted pollutant accumulating capacity. Considerable differences in pH, electrical conductivity, bulk density, and water-holding capacity were observed between the soil receiving effluent discharge and solid waste dumping and the control soil. The soil had accumulated considerable amounts of the exchangeable cations (Ca, Mg, Na, and K). The work has found that industrial activities have worked against the normal behavior of the soil and reduced its capacity to serve as a natural repository of carbon.