Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Genotoxicity of chromium in vitro on yeast: Interaction with DNA†

The genotoxicity of chromium chloride was investigated in cells of D₇ strain of Saccharomyces cerevisiae harvested either from logarithmic or stationary growth phase.

A weak induction of mifotic gene conversion and point reverse mutation was obtained when the incubations were performed using phosphate buffer. No genetic effect was observed when the incubations were performed using Tris‐HCl buffer.

The experiments with ⁵¹Cr radiotracer demonstrated that Cr³⁺ ion enters the yeast cells and binds to DNA even if the incubation mixture was performed with Tris HCl buffer. This behaviour could be due to the highest concentration of CrCl₃ that cause some damages to cytoplasmatic membrane.     

Chromium exhibits adverse effects at environmental relevant concentrations in chronic toxicity assay system of nematode Caenorhabditis elegans

Here we investigated whether the assay system (10-d) in Caenorhabditis elegans can be used to evaluate chronic toxicity of chromium (Cr(VI)) at environmental relevant concentrations ranging from 5.2 μg L⁻¹ to 260 μg L⁻¹. The results indicated that lethality, locomotion behavior as revealed by head thrash, body bend, and forward turn, metabolism as revealed by pumping rate and mean defecation cycle length, intestinal autofluorescence, and ROS production were severely altered in Cr chronically exposed nematodes at environmental relevant concentrations. The most surprising observations were that head thrash, body bend, intestinal autofluorescence, and ROS production in 13 μg L⁻¹ Cr exposed nematodes were significantly influenced. The observed adverse effects of Cr on survival, locomotion behavior, and metabolism were largely due to forming severe intestinal autofluorescence and ROS production. Therefore, our findings demonstrate the usefulness of chronic toxicity assay system in C. elegans in evaluating the chronic toxicity of toxicants at environmental relevant concentrations.     

Synthesis of hydrogarnet from molten slag and its hydrogen chloride fixation performance at high temperature

Hydrogarnet was synthesized hydrothermally below 200°C using molten slag obtained from municipal solid waste. For comparison, it was also synthesized using pure-phase CaO–Al₂O₃–SiO₂–H₂O, as reported previously. The structural and textural properties of this material were investigated using various analytical and spectroscopic techniques such as X-ray diffraction, X-ray fluorescence spectrometry, atomic absorption spectrometry (AAS), thermogravimetry/differential thermal analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. The Cl⁻ fixation ability of hydrogarnet was investigated in the temperature range 500–800°C in a fixed-bed flow reactor using a HCl concentration (1000 p.p.m.v.) similar to that of incinerator exhaust gas. Under these experimental conditions, the hydrogarnet was capable of reducing the HCl gas level to less than 1 p.p.m.v. Analysis of the spent catalyst revealed that the hydrogarnet was being transformed into wadalite and CaCl₂ at high temperatures. The elution test for chromium ions in hydrogarnet obtained from slag was also used, and it was found that chromium ions were not eluted from hydrogarnet. Received: January 27, 2001 / Accepted: October 11, 2001     

Changes of organic acid exudation and rhizosphere pH in rice plants under chromium stress.

The effect of chromium (Cr) stress on the changes of rhizosphere pH, organic acid exudation, and Cr accumulation in plants was studied using two rice genotypes differing in grain Cr accumulation. The results showed that rhizosphere pH increased with increasing level of Cr in the culture solution and with an extended time of Cr exposure. Among the six organic acids examined in this experiment, oxalic and malic acid contents were relatively higher, and had a significant positive correlation with the rhizosphere pH, indicating that they play an important role in changing rhizosphere pH. The Cr content in roots was significantly higher than that in stems and leaves. Cr accumulation in plants was significantly and positively correlated with rhizosphere pH, and the exudation of oxalic, malic and citric acids, suggesting that an increase in rhizosphere pH, and exudation of oxalic, malic and citric acid enhances Cr accumulation in rice plants.     

Removal of hexavalent chromium from water by Z-scheme photocatalysis using TiO2 (rutile) nanorods loaded with Au core–Cu2O shell particles

All-solid-state Z-scheme photocatalysts, containing Cu₂O, TiO₂ (rutile), and Au as the electron mediator, were prepared and applied to the reduction of Cr(VI) in aqueous solutions. The Cu₂O–Au–TiO₂ composites were prepared by loading Au core–Cu₂O shell hemisphere particles on TiO₂ (rutile) nanorods using a two-step photocatalytic deposition process. Under ultraviolet–visible (UV–vis) light illumination, the Cu₂O–Au–TiO₂ composites exhibited higher photocatalytic Cr(VI) reduction activities than those exhibited by single TiO₂ (rutile) and Cu₂O. In this reaction, a precipitate containing Cr, which was considered to be Cr(OH)₃, was deposited site-selectively on the Au core–Cu₂O shell particles of the composites, indicating that the reduction site of the composite was Cu₂O, and the reaction proceeded according to the Z-scheme. The Cu₂O–Au–TiO₂ composites also exhibited photocatalytic activity under visible light illumination. The oxidation state of Cu in the Cu₂O–Au–TiO₂ composite gradually changed from Cu(I) to Cu(II) during the photocatalytic Cr(VI) reduction. However the composite maintained its high photocatalytic performance even after oxidation. The role of Au in the Cu₂O–Au–TiO₂ composite was examined by comparing the properties of the Cu₂O–Au–TiO₂ composite with those of the Cu₂O–TiO₂ composite prepared via direct Cu₂O deposition on TiO₂.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

The role of humic substances in chromium sorption onto natural organic matter (peat)

To elucidate mechanisms of Cr³⁺ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000–1000 μm, 630–200 μm and 63–20 μm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC_t confirmed that for cation exchange capacity were responsible mainly cations connected with COO⁻ functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr³⁺ binding, thus the finest studied fraction 63–20 μm of the highest contents of functional groups showed the lowest sorption capacity for Cr³⁺, while similar patterns of sorbed Cr³⁺, soluble HS content and base CEC₀ indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC₀ (with Ca²⁺ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr³⁺ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr³⁺-organic compounds.     

Spatial and temporal variability of water repellency in a sandy soil contaminated with tar oil and heavy metals

Water repellency can induce preferential flow and thus affect water flow and contaminant transport at hazardous waste sites. Since the spatial patterns of water repellency are mostly unknown, it is problematic to use numerical transport models to predict leachate composition. In this study, the spatial variability of soil water repellency was studied at an industrial site contaminated with tar oil, chromium, copper and arsenic. The persistence of water repellency was assessed by the water drop penetration time (WDPT), and the degree of water repellency was quantified by the ethanol percentage (EP) test. Measurements were made at the soil surface along 3.5-12.1 m long transects at different times between March and October 2002. The spatial variability of WDPT, EP, water content, and organic matter content was quantified by variogram analyses. Both the persistence and the degree of water repellency varied seasonally, with the highest water repellency during the summer months. The correlation lengths of WDPT values ranged between 16 and 406 cm, whereas EP values showed no spatial correlation. For field-moist samples, a critical soil water threshold, below which water repellency prevails, was estimated to be 2.5-4%. For oven dry samples, the WDPT values were dependent on the water content prior to drying. The wide range of correlation lengths and the temporal dynamics of spatial repellency patterns suggest that simulations of solute leaching must consider the spatial and temporal variability of soil hydrophobic properties.