Zlatna, Romania is the site of longtime mining/smelting operations which have resulted in widespread metal pollution of the entire area. Previous studies have documented the contamination using traditional methods involving soil sample collection, digestion, and quantification via inductively coupled plasma atomic emission spectroscopy or atomic absorption. However, field portable X-ray fluorescence spectroscopy (PXRF) can accurately quantify contamination in-situ, in seconds. A PXRF spectrometer was used to scan 69 soil samples in Zlatna across multiple land use types. Each site was georeferenced with data inputted into a geographic information system for high resolution spatial interpolations. These models were laid over contemporary aerial imagery to evaluate the extent of pollution on an individual elemental basis. Pb, As, Co, Cu, and Cd exceeded governmental action limits in >50% of the sites scanned. The use of georeferenced PXRF data offers a powerful new tool for in-situ assessment of contaminated soils.

The aim of this novel research was to determine the toxic burden of increased elements in water resources on the inhabitant wild animals (squirrels, turtles, bats), using particle induced x-ray emission (PIXE) and histopathological approaches. PIXE analysis of skin, muscle, lung, liver and kidney revealed significant increase in Al, Cl, Fe, Mg, Mn, Si and V. Moreover, data clearly reflect a significant (P < 0.001) deposition of toxic elements (Al, Cl, Fe and K) in the lung producing interstitial/proliferative pneumonitis, intra-alveolar hemorrhages, and thickening of alveolar capillary walls. The results obtained from the liver samples emphasized that majority of the animals were intoxicated with Cl, Mg, S, Si and V, which have produced profound deterioration and swelling of the hepatocytes. Likewise, histopathology of the kidney sections spotlighted severe nephritis and degenerative changes, which could be associated with the elevated amount of Al, Cl and Mg. This data undoubtedly provide relevant information on the heavy burden of toxic elements and their pathological outcomes in wild animals and highlight their potential risks for human exposure. Thus, the information provided is critical for developing effective strategies in dealing with health hazards associated with elemental exposures.

The aim of this study was the multi-elemental detection of toxic metals such as lead (Pb) in non-crushed oyster shells by using a portable X-ray fluorescence (XRF) spectrometer. A rapid, simultaneous multi-element analytical methodology for non-crushed oyster shells has been developed using a portable XRF which provides a quick, quantitative, non-destructive, and cost-effective mean for assessment of oyster shell contamination from Pb. Pb contamination in oyster shells was further confirmed by scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). The results indicated that Pb is distributed in-homogeneously in contaminated shells. Oyster shells have a lamellar structure that could contribute to the high accumulation of Pb on oyster shells.

The effect of lead on the sorption of 2,4,6-trichlorophenol (2,4,6-TCP) on soil and peat was investigated using a batch equilibration method. Lead markedly diminished the sorption of 2,4,6-TCP, and 2,4,6-TCP had little effect on lead sorption. Peat was a more effective adsorbent for 2,4,6-TCP than soil. The desorption hysteresis of 2,4,6-TCP verified the presence of high-energy sorption sites. Mechanisms of lead suppression effect on the 2,4,6-TCP sorption included the following: Firstly, lead accelerated the aggregation of colloids, the aggregates covered the surface in part and shrunk the pore sizes of the adsorbents, hence decreased the sorption of 2,4,6-TCP. Secondly, X-ray absorption and Fourier transform infrared spectroscopy study suggested that lead competed with 2,4,6-TCP for carboxylic, phenolic and Si-OH groups of organic matter and clay minerals. Such competition was partly responsible for the overall suppression effect of lead on the sorption of 2,4,6-TCP. Lead diminished the sorption of 2,4,6-trichlorophenol onto soil and peat.

The effectiveness and mechanism of nano-hydroxyapatite particles (nHAp) in immobilizing Pb and Cd from aqueous solutions and contaminated sediment were investigated. The maximum sorption amount (Qmax) of Pb and Cd in aqueous solution was 1.17 and 0.57 mmol/g. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) surface and depth analysis indicated that dissolution-precipitation is the primary immobilization mechanism for Pb, while surface complexation and intraparticle diffusion account for Cd sequestration. Different amounts of nHAp (0–10% nHAp/dry weight) were added to the contaminated sediment. Sequential extraction showed that nHAp could effectively reduce the exchangeable fraction of Pb and Cd in the sediment and significantly reduce the concentration in porewater. The results in this study showed that nHAp can immobilize Pb and Cd in sediment effectively. Nano-hydroxyapatite shows potential and advantages to immobilize lead and cadmium in aqueous solution and sediment.

The effects of confounding by temporal factors remains understudied in pollution ecology. For example, there is little understanding of how disturbance history affects the development of assemblages. To begin addressing this gap in knowledge, marine biofilms were subjected to temporally-variable regimes of copper exposure and depuration. It was expected that the physical and biological structure of the biofilms would vary in response to copper regime. Biofilms were examined by inductively coupled plasma optical emission spectrometry, chlorophyll-a fluorescence and field spectrometry and it was found that (1) concentrations of copper were higher in those biofilms exposed to copper, (2) concentrations of copper remain high in biofilms after the source of copper is removed, and (3) exposure to and depuration from copper might have comparable effects on the photosynthetic microbial assemblages in biofilms. The persistence of copper in biofilms after depuration reinforces the need for consideration of temporal factors in ecology.

Extracellular polymeric substances (EPS) are, along with microbial cells, the main components of the biological sludges used in wastewater treatment and natural biofilms. EPS play a major role in removing pollutants from water by means of sorption. The ability of soluble EPS (S-EPS) and bound EPS (B-EPS) derived from various bacterial aggregates (flocs, granules, biofilms) to bind at pH 7.0 ± 0.1 to two pharmaceutical substances, acetaminophen (ACE) and erythromycin ethylsuccinate (ERY), has been investigated using the fluorescence quenching method. Two intense fluorescence peaks, A (Ex/Em range, 200-250/275-380 nm) and B (Ex/Em range, 260-320/275-360 nm), corresponding respectively to the aromatic protein region and soluble microbial by-product-like region, were identified in a three-dimensional excitation-emission matrix of EPS samples. The fluorescence peak, which corresponds to humic-like substances, was also identified though at low intensity. The ability of EPS to bind ACE was found to exceed that for ERY. The aromatic protein fraction of EPS displays a slightly higher affinity for drugs than that shown by the soluble microbial by-product-like fraction. The S-EPS and B-EPS present the same affinity for ACE and ERY. The effective quenching constants (log K) derived from the Stern-Volmer Equation equaled at peak A (with S-EPS): 3.7 ± 0.2 to 4.0 ± 0.1 for ACE and 2.1 ± 0.3 to 2.7 ± 0.1 for ERY. With B-EPS, these values were 3.9 ± 0.1 to 4.0 ± 0.1 for ACE and 2.0 ± 0.2 to 2.6 ± 0.1 for ERY. Our results suggest that the weaker EPS affinity for ERY than for ACE serves to partially explain why only about 50-80 % of ERY is removed from wastewater at the treatment plant. Moreover, this work demonstrates that EPS from natural river biofilms are able to bind drugs, which in turn may limit the mobility of drugs in natural waters.

PURPOSE: The purpose this research is to investigate the interaction of Cr(VI) species, present as Cr₂O₇ ²⁻, at ambient temperature with brick clay pre-fired at different temperatures. METHODS: A multi-technique approach was used for this investigation. Experiments such as surface titrations, Langmuir and Freundlich adsorption isotherms, mass-firing temperature investigation, scanning electron microscopy, Fourier transform infrared spectra, X-ray fluorescence spectra, and X-ray diffraction were conducted in this investigation. RESULTS: Fired brick clay, which bears a negative charge according to surface titration measurements, shows affinity towards Cr(VI) species despite the negative charge of the source of Cr(VI). The Cr(VI)—brick clay heterogeneous system, which shows the strongest interaction with brick clay fired at 200°C, obeys both the Langmuir and the Freundlich adsorption isotherms with high regression coefficients. Investigation on surface charge, constituents of brick clay, acid treatment of clay particles, and the effect of firing temperature suggests that the reduction of Cr(VI) to Cr(III) by reducing agents present in brick clay makes a significant contribution for adsorption of chromium species followed by subsequent removal. Scanning electron microscopic images support the adsorption of chromium species, and further, many metal ions are released as a result of Cr(VI)—brick clay interaction according to X-ray fluorescence studies. CONCLUSION: It is concluded that fired brick clay shows strong adsorption capacity on Cr(VI), having the maximum interaction with brick clay fired at 200°C. It is proposed that this methodology be extended for treatment of effluents containing Cr(VI) species.