Spatiotemporal evolution of soil pH and zinc after the Aznalcollar mine spill

The residual pollution after the Aznalcóllar (southwestern Spain) pyrite mine spill is still a threat due to the continuing oxidation of sulfuric minerals. The objective of this paper was to analyze the combined effect of pyrite oxidation, sugar beet foam applications, and meteorological conditions on the spatiotemporal evolution of the pH and EDTA-extractable Zn concentration, using non co-located data from 11 sampling dates between June 1999 and March 2002. Median pH values ranged from 4.4 at the beginning of the monitoring period to 7.6 at the end, although values near 2.5 were observed throughout the entire period, despite of two sugar beet foam (SBF) applications. Zinc distributions were positively skewed and median concentrations ranged from 17 to 94 mg kg(-1). The inverse relationship between pH and Zn became weaker toward the end of the monitoring period as a consequence of the precipitation and posterior dissolution of newly formed minerals from the reaction products of the pyrite oxidation. Normal score maps showed that after the SBF applications only 0.5% of the monitored area was below the pH = 4 threshold, while on other dates up to one-third of the area remained below this value. The better performance of the second SBF application could be explained in terms of pyrite oxidation pathways and environmental conditions. From this analysis, with data obtained under uncontrolled field conditions, it is concluded that SBF should be applied before or during the wet and cold season to alleviate acidification, caused by the oxidation of pyrite or other sulfuric minerals.     

Passive air sampling theory for semivolatile organic compounds

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.     

Biological assessment of bisphenol A degradation in water following direct photolysis and UV advanced oxidation

Endocrine disrupting compounds (EDCs) are exogenous environmental chemicals that can interfere with normal hormone function and present a potential threat to both environmental and human health. The fate, distribution and degradation of EDCs is a subject of considerable investigation. To date, several studies have demonstrated that conventional water treatment processes are ineffective for removal of most EDCs and in some instances produce multiple unknown transformation products. In this study we have investigated the use of direct photolysis with low-pressure (LP) Hg UV lamps and UV+hydrogen peroxide (H(2)O(2)) advanced oxidation process (AOP) for the degradation of a prototypic endocrine disrupter, bisphenol A (BPA), in laboratory water. Removal rates of BPA and formation of degradation products were determined by high performance liquid chromatography (HPLC) analysis. Changes in estrogenic activity were evaluated using both in vitro yeast estrogen screen (YES) and in vivo vitellogenin (VTG) assays with Japanese medaka fish (Oryzias latipes). Our results demonstrate that UV alone did not effectively degrade BPA. However, UV in combination with H(2)O(2) significantly removed BPA parent compound and aqueous estrogenic activity in vitro and in vivo. Removal rates of in vivo estrogenic activity were significantly lower than those observed in vitro, demonstrating differential sensitivities of these bioassays and that certain UV/AOP metabolites may retain estrogenic activity. Furthermore, the UV/H(2)O(2) AOP was effective for reducing larval lethality in treated BPA solutions, suggesting BPA degradation occurred and that the degradation process did not result in the production of acutely toxic intermediates.     

Efficient retrieval of vegetation leaf area index and canopy clumping factor from satellite data to support pollutant deposition assessments

Canopy leaf area index (LAI) is an important structural parameter of the vegetation controlling pollutant uptake by terrestrial ecosystems. This paper presents a computationally efficient algorithm for retrieval of vegetation LAI and canopy clumping factor from satellite data using observed Simple Ratios (SR) of near-infrared to red reflectance. The method employs numerical inversion of a physics-based analytical canopy radiative transfer model that simulates the bi-directional reflectance distribution function (BRDF). The algorithm is independent of ecosystem type. The method is applied to 1-km resolution AVHRR satellite images to retrieve a geo-referenced data set of monthly LAI values for the conterminous USA. Satellite-based LAI estimates are compared against independent ground LAI measurements over a range of ecosystem types. Verification results suggest that the new algorithm represents a viable approach to LAI retrieval at continental scale, and can facilitate spatially explicit studies of regional pollutant deposition and trace gas exchange.