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.

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 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 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 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.

Beta blockers are widely used pharmaceuticals that have been detected in the environment. Interactions between beta blockers and dissolved organic matter (DOM) may mutually alter their environmental behaviors. To assess this potential, propranolol (PRO) was used as a model beta blocker to quantify the complexation with DOM from different sources using the fluorescence quenching titration method. The sources of studied DOM samples were identified by excitation–emission matrix spectroscopy (EEMs) combined with fluorescence regional integration analysis. The results show that PRO intrinsic fluorescence was statically quenched by DOM addition. The resulting binding constants (log Kₒc) ranged from 3.90 to 5.20, with the surface-water-filtered DOM samples claiming the lower log Kₒcand HA having the highest log Kₒc. Log Kₒcis negatively correlated with the fluorescence index, biological index, and the percent fluorescence response (P ᵢ,ₙ) of protein-like region (PI,ₙ) and the P ᵢ,ₙof microbial byproduct-like region (PII,ₙ) of DOM EEMs, while it is correlated positively with humification index and the P ᵢ,ₙof UVC humic-like region (PIII,ₙ). These results indicate that DOM samples from allochthonous materials rich in aromatic and humic-like components would strongly bind PRO in aquatic systems, and autochthonous DOM containing high protein-like components would bind PRO more weakly.

Selected water quality parameters and spectroscopic characteristics of dissolved organic matter (DOM) were examined during two different seasons for an artificial coastal lake (Shiwha Lake in South Korea), which are affected by seawater exchange due to the operation of a tidal power plant and external organic loadings from the upstream catchments. The coastal lake exhibited much lower concentrations of organic matter and nutrients than the upstream sources. The spectroscopic properties of the lake DOM were easily distinguished from those of the catchment sources as revealed by a lower absorption coefficient, lower degree of humification, and higher spectral slopes. The observed DOM properties suggest that the lake DOM may be dominated by smaller molecular size and less condensed structures. For the lake and the upper streams, higher absorption coefficients and fluorescence peak intensities but lower spectral slopes and humification index were found for the premonsoon versus the monsoon season. However, such seasonal differences were less pronounced for the industrial channels in the upper catchments. Three distinctive fluorophore groups including microbial humic-like, tryptophan-like, and terrestrial humic-like fluorescence were decomposed from the fluorescence excitation-emission matrix (EEM) of the DOM samples by parallel factor analysis (PARAFAC) modeling. The microbial humic-like component was the most abundant for the industrial channels, suggesting that the component may be associated with anthropogenic organic pollution. The terrestrial humic-like component was predominant for the upper streams, and its relative abundance was higher for the rainy season. Our principal component analysis (PCA) results demonstrated that exchange of seawater and seasonally variable input of allochthonous DOM plays important roles in determining the characteristics of DOM in the lake.

Different land uses of upstream catchments may affect the quantity and the quality of dissolved organic matter (DOM) in watersheds, but the influence may differ by season. In this study, we examined concentrations and selected spectroscopic properties of DOM and the propensity to form trihalomethanes (THMs) for 19 different middle-sized watersheds across the Han River basin in Korea. Sampling was conducted for non-storm events during pre-monsoon (May) and monsoon seasons (July). The anthropogenic land uses including agricultural and residential areas occupied 2.3 to 49.4 % of the upstream catchments of the watersheds. Non-aromatic, labile, and less condensed DOM structures were more abundant in the monsoon season. Parallel factor analysis (PARAFAC) modeling with fluorescence data demonstrated that a combination of three different fluorescence components could explain the seasonal and the spatial distributions of DOM characteristics. Terrestrial humic-like fluorescence was the most abundant component for all the DOM samples, while protein-like fluorescence became more pronounced for the monsoon season. THM concentrations did not differ between the two seasons. Observed seasonal differences in the concentrations and the characteristics of DOM suggested a greater contribution of groundwater to the streams in watersheds in the monsoon versus the pre-monsoon season. Significant correlations among anthropogenic land use, microbial humic-like fluorescence, and the propensity to form THMs were found only for the pre-monsoon season. Principal component analysis (PCA) demonstrated that, regardless of the season, anthropogenic land uses increased the concentrations of DOM and nutrients but that their effects on the DOM properties were not evident for the monsoon season.