Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

Development of aquatic life criteria in China: viewpoint on the challenge

While more developed countries have a well-established systems to develop water quality criteria (WQC), little research has been done on the adequacy of the current WQC to protect endemic species of China. In order to maintain the health of aquatic ecosystems in China, a series of projects to establish national WQC based on regional characteristics has recently been initiated. However, the establishment of a completely novel methodology would be costly and time consuming. Also, due to the similarities in physiologies and natural histories of classes of aquatic organisms, there is no reason to believe that WQC would not be sufficient to protect unique species in China. This review was undertaken to identify key outstanding issues regarding establishment of aquatic life criteria (ALC) to be applied in China, including prioritization of chemicals, test species, mode of action, field/semi-field data, and methods of aggregating the information and calculating the ALC. This was used to identify the principle issues that need to be addressed in order to better understand the methods for development of criteria for the protection of aquatic life and provide a reference to China and other developing countries committed to the establishment of their own WQC system.     

A comparison of statistical methods for deriving freshwater quality criteria for the protection of aquatic organisms

Species sensitivity distributions (SSDs) are increasingly used in both ecological risk assessment and derivation of water quality criteria. However, there has been debate about the choice of an appropriate approach for derivation of water quality criteria based on SSDs because the various methods can generate different values. The objective of this study was to compare the differences among various methods. Data sets of acute toxicities of 12 substances to aquatic organisms, representing a range of classes with different modes of action, were studied. Nine typical statistical approaches, including parametric and nonparametric methods, were used to construct SSDs for 12 chemicals. Water quality criteria, expressed as hazardous concentration for 5 % of species (HC₅), were derived by use of several approaches. All approaches produced comparable results, and the data generated by the different approaches were significantly correlated. Variability among estimates of HC₅ of all inclusive species decreased with increasing sample size, and variability was similar among the statistical methods applied. Of the statistical methods selected, the bootstrap method represented the best-fitting model for all chemicals, while log-triangle and Weibull were the best models among the parametric methods evaluated. The bootstrap method was the primary choice to derive water quality criteria when data points are sufficient (more than 20). If the available data are few, all other methods should be constructed, and that which best describes the distribution of the data was selected.     

The amorphous Zn biomineralization at Naracauli stream,Sardinia: electron microscopy and X-ray absorption spectroscopy

An amorphous Zn biomineralization (“white mud”), occurring at Naracauli stream, Sardinia, in association with cyanobacteria Leptolyngbya frigida and diatoms, was investigated by electron microscopy and X-ray absorption spectroscopy. Preliminary diffraction analysis shows that the precipitate sampled on Naracauli stream bed is mainly amorphous, with some peaks ascribable to quartz and phyllosilicates, plus few minor unattributed peaks. Scanning electron microscopy analysis shows that the white mud, precipitated in association with a seasonal biofilm, is made of sheaths rich in Zn, Si, and O, plus filaments likely made of organic matter. Transmission electron microscopy analysis shows that the sheaths are made of smaller units having a size in the range between 100 and 200 nm. X-ray absorption near-edge structure and extended X-ray absorption fine structure data collected at the Zn K-edge indicate that the biomineral has a local structure similar to hemimorphite, a zinc sorosilicate. The differences of this biomineral with respect to the hydrozincite biomineralization documented about 3 km upstream in the same Naracauli stream may be related to either variations in the physicochemical parameters and/or different metabolic behavior of the involved biota.     

Modelling remediation scenarios in historical mining catchments

Local remediation measures, particularly those undertaken in historical mining areas, can often be ineffective or even deleterious because erosion and sedimentation processes operate at spatial scales beyond those typically used in point-source remediation. Based on realistic simulations of a hybrid landscape evolution model combined with stochastic rainfall generation, we demonstrate that similar remediation strategies may result in differing effects across three contrasting European catchments depending on their topographic and hydrologic regimes. Based on these results, we propose a conceptual model of catchment-scale remediation effectiveness based on three basic catchment characteristics: the degree of contaminant source coupling, the ratio of contaminated to non-contaminated sediment delivery, and the frequency of sediment transport events.     

A robust simulation–optimization modeling system for effluent trading—a case study of nonpoint source pollution control

In this study, a robust simulation–optimization modeling system (RSOMS) is developed for supporting agricultural nonpoint source (NPS) effluent trading planning. The RSOMS can enhance effluent trading through incorporation of a distributed simulation model and an optimization model within its framework. The modeling system not only can handle uncertainties expressed as probability density functions and interval values but also deal with the variability of the second-stage costs that are above the expected level as well as capture the notion of risk under high-variability situations. A case study is conducted for mitigating agricultural NPS pollution with an effluent trading program in Xiangxi watershed. Compared with non-trading policy, trading scheme can successfully mitigate agricultural NPS pollution with an increased system benefit. Through trading scheme, [213.7, 288.8]?×?10³ kg of TN and [11.8, 30.2]?×?10³ kg of TP emissions from cropped area can be cut down during the planning horizon. The results can help identify desired effluent trading schemes for water quality management with the tradeoff between the system benefit and reliability being balanced and risk aversion being considered.     

Micropollutants in urban stormwater: occurrence,concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments

This study aimed at: (a) providing information on the occurrence and concentration ranges in urban stormwater for a wide array of pollutants (n?=?77); (b) assessing whether despite the differences between various catchments (land use, climatic conditions, etc.), the trends in terms of contamination level are similar; and (c) analyzing the contribution of total atmospheric fallout (TAF) with respect to sources endogenous to this contamination. The studied contaminants include conventional stormwater contaminants (polycyclic aromatic hydrocarbons (PAHs), Zn, Cu, Pb, etc.), in addition to poorly or undocumented pollutants such as nonylphenol and octylphenol ethoxylates (NPnEO and OPnEO), bisphenol A (BPA), polybrominated diphenyl ethers (PBDEs), a wide variety of pesticides, and various metals of relevance (As, Ti, Sr, V). Sampling and analysis were performed using homogeneous methods on three urban catchments with different land use patterns located in three distinct French towns. For many of these pollutants, the results do not allow highlighting a significant difference in stormwater quality at the scale of the three urban catchments considered. Significant differences were, however, observed for several metals (As, Cr, Cu, Ni, Sr and Zn), PAHs, and PBDEs, though this assessment would need to be confirmed by further experiments. The pollutant distributions between dissolved and particulate phases were found to be similar across the three experimental sites, thus suggesting no site dependence. Lastly, the contributions of TAF to stormwater contamination for micropollutants were quite low. This finding held true not only for PAHs, as previously demonstrated in the literature, but also for a broader range of molecules such as BPA, NPnEO, OPnEO, and PBDEs, whose high local production is correlated with the leaching of urban surfaces, buildings, and vehicles.     

Impacts on effluent contaminants from mine sites: risk assessment,fate, and distribution of pollution at basin scale

The environmental implications of mining activities are of worldwide concern. An environmental evaluation at the basin level was conducted because of widespread mining in Cajamarca in Northern Peru. A sediment monitoring program was developed at the Jequetepeque basin, located in Cajamarca. A total of 16 sites were monitored at three different times between June 2009 and July 2010, and a total of 42 samples were collected. All samples were analyzed by microwave digestion and by a sequential extraction scheme following the three-stage European Community Bureau of Reference (three-stage BCR) protocol. Trace element mobilization from the sediments to the water column was assessed by the risk assessment code (RAC). Spatial and temporal distribution of trace elements was evaluated by principal component analysis and hierarchical cluster analysis. Cd, Zn, As, and Pb showed the highest concentrations independent of season. Notably, Cu concentration and mobility increased during the wet season for all samples. Additionally, Hg concentration and mobility increased during the wet season near the mine sites. According to the enrichment factor, the highest enrichments of Cd, Zn, Pb, and As were related to mine runoff. The effect of trace elements near the mine sites at the Jequetepeque basin was considered a significant threat to the environment due to Cd, Zn, Pb, and As, and the concentrations of Cu and Hg were also considered a concern. This work establishes a baseline for the environmental quality status of the Jequetepeque basin that may support water quality management in Peru.     

Mass loads of dissolved and particulate mercury and other trace elements in the Mt. Amiata mining district,Southern Tuscany (Italy)

Total dissolved and particulate mercury (Hg), arsenic (As), and antimony (Sb) mass loads were estimated in different seasons (March and September 2011 and March 2012) in the Paglia River basin (PRB) (central Italy). The Paglia River drains the Mt. Amiata Hg district, one of the largest Hg-rich regions worldwide. Quantification of Hg, As, and Sb mass loads in this watershed allowed (1) identification of the contamination sources, (2) evaluation of the effects of Hg on the environment, and (3) determination of processes affecting Hg transport. The dominant source of Hg in the Paglia River is runoff from Hg mines in the Mt. Amiata region. The maximum Hg mass load was found to be related to runoff from the inactive Abbadia San Salvatore Mine (ASSM), and up to 30 g day^?1 of Hg, dominantly in the particulate form, was transported both in high and low flow conditions in 2011. In addition, enrichment factors (EFs) calculated for suspended particulate matter (SPM) were similar in different seasons indicating that water discharge controls the quantities of Hg transported in the PRB, and considerable Hg was transported in all seasons studied. Overall, as much as 11 kg of Hg are discharged annually in the PRB and this Hg is transported downstream to the Tiber River, and eventually to the Mediterranean Sea. Similar to Hg, maximum mass loads for As and Sb were found in March 2011, when as much as 190 g day^?1 each of As and Sb were measured from sites downstream from the ASSM. Therefore, the Paglia River represents a significant source of Hg, Sb, and As to the Mediterranean Sea.     

Reproductive toxicity of lead,cadmium, and phthalate exposure in men

Environmental toxicants viz lead or cadmium and phthalate esters (di(2-ethylhexyl) phthalate [DEHP], dibutyl phthalate [DBP], and diethyl phthalate [DEP]) widely found in different environmental strata are linked to deteriorating male reproductive health. The objective was to assess the relationships between the seminal lead, cadmium, and phthalate (DEHP, DBP, DEP) concentrations at environmental level and serum hormone levels and semen quality in non-occupationally exposed men and specify the effect of individual and combined exposure of toxicants on semen quality. A study of 60 male partners of couples attending the Andrology Laboratory of the Reproductive Biology Department, All India Institute of Medical Sciences (AIIMS), New Delhi, India for semen analysis to assess their inability to achieve a pregnancy was selected for the study. The results of univariate and stepwise multiple regression analysis in the unadjusted model showed a significant correlation between lead or cadmium and phthalates DEHP/DBP/DEP and sperm motility, sperm concentration, and DNA damage. After adjusting for potential confounders, an association with lead or DEHP was only observed. The present data shows that lead (Pb) or cadmium (Cd) or phthalates might independently contribute to decline in semen quality and induce DNA damage. Phthalates might influence reproductive hormone testosterone. These findings are significant in light of the fact that men are exposed to a volley of chemicals; however, due to the small sample size, our finding needs to be confirmed in a larger population.