A model of natural degradation of 17-α-ethinylestradiol in surface water and identification of degradation products by GC-MS

Over the past decade, the environment has been polluted by a wide spectrum of exogenous chemicals and environmental analysis has become one of the most progressive parts of analytical research. The aim of this work was to determine the kinetics of natural degradation, and to identify the degradation products of the massively used estrogenic drug, 17-α-ethinylestradiol. The photodegradation, oxidation and thermostability conditions were selected according to ICH requirements for pharmaceutical stability testing. A simple 72-h photodegradation study in purified water exhibited significant first-order kinetics with the kinetic constant k = 0.0303 h^?1, and degradation halftime 22.8 h. The basic halftime could be reduced to 17.1 h by the addition of sea salt, and increase in temperature. Monohydroxy, dihydroxy and dehydrogenated derivatives of ethinylestradiol with intact steroidal structure were identified as major degradation products resulting from simple photodegradation. The addition of an oxidative agent significantly accelerated the degradation rate; combined with higher temperature, the degradation halftime was reduced to 1.1 h with the first-order kinetic constant k = 0.632 h^?1. TOC analysis showed a notable decrease of organic mass (18% in 3 days) during oxidation experiments, and confirmed the degradation of steroidal structure.

     

Organochlorine concentrations in franciscana dolphins, Pontoporia blainvillei, from Brazilian waters

Blubber samples were collected from ten franciscana dolphins either incidentally captured in fishing operations or stranded on São Paulo (SP) and Paraná (PR) states littoral, Southeastern and Southern Brazilian coast, respectively. Determination of PCB, DDT and HCB concentrations were performed by capillary gas chromatograph coupled to electron capture detector (ECD). ΣDDT, ΣPCB and HCB concentrations ranged from 264 ng g⁻¹ to 5811 ng g⁻¹ lipid, from 909 ng g⁻¹ to 5849 ng g⁻¹ lipid and from 10 ng g⁻¹ to 61 ng g⁻¹ lipid, respectively. Regarding DDTs, the distribution of the mean percentages decreased in the following order: p,p′-DDE > p,p′-DDD > p,p′-DDT. The ΣDDT/ΣPCB ratio varied between 0.27 and 0.42 in Northern and Central SP coast, while in Southern SP and PR coast the values were 1.6 and 1.9, respectively. Dissimilarities in ΣDDT/ΣPCB ratios point to different sources of organochlorine compounds to franciscana dolphins in the study area. Considering the endocrine disruptive action of organochlorine compounds, the concentrations found in franciscana dolphins from Brazilian waters may represent an additional obstacle to the conservation of this endangered cetacean species.     

Measurement of gas diffusion through soils: comparison of laboratory methods

Gas movement through soils is important for ecosystems and engineering in many ways such as for microbial and plant respiration, passive methane oxidation in landfill covers and oxidation of mine residues. Diffusion is one of the most important gas movement processes and the determination of the diffusion coefficient is a crucial step in any study. Five laboratory methods used for measuring the relative gas diffusion coefficient (D(s)/D(o)) were compared using a loamy sand, a porous media commonly found in agricultural fields and in several engineered structures, such as in landfill final covers. In the absence of macropores, all methods gave rather similar values of D(s)/D(o). Methods allowing the study of microscale variability indicated that the presence of macropores highly influenced gas movement, thus the value of D(s)/D(o), which, near a macropore may be one order of magnitude higher than in regions without macropores. Repacked columns do not allow the study of heterogeneity in D(s)/D(o). Natural spatial variability in D(s)/D(o) due to water distribution and preferential pathways can only be studied in large systems, but these systems are difficult to handle. Advantages and disadvantages of each method are discussed.     

Associations between urinary cadmium levels,blood pressure,and hypertension: the ESTEBAN survey

Environmental Science and Pollution Research - Cadmium is inconsistently associated with blood pressure (BP) and hypertension. Our study focuses to understand the association between urinary...     

Assessment of groundwater quality in a region of endemic fluorosis in the northeast of Brazil

The aim of this study was to estimate the risk for caries and fluorosis in a desertification area, applying the calcium/fluoride concentration ratio of underground water and the quality of water in a selected geographical region. This study was performed in the municipality of São João do Rio do Peixe, located in the tropical semiarid lands of Brazil. A total of 111 groundwater samples were collected. Fluoride concentration varied from 0.11 to 9.33 mg/L. Thirty percent of all samples analyzed showed values above 1.5 mg/L, while 64 % were above the ideal limit of 0.7 mg/L. Mean calcium concentration was 47.6 mg/L, and 14.4 % of all samples presented values above the WHO acceptable limits. The proportional value of calcium/fluoride in water showed that only 12 % of the samples were suitable for dental caries prevention with minimal risk for dental fluorosis. Mapping of the fluoride distribution indicated that approximately 2,465 people could be affected by dental fluorosis and 1,057 people might be affected by skeletal fluorosis. It can be concluded that, in addition to fluoride, many water parameters were not suitable for the drinking water. Mapping out calcium/fluoride ratio may indicate areas of water suitability for caries control, whereas the fluoride concentration solely can indicate the areas with the risk for fluorosis. This approach can be relevant for health authorities for identifying communities where dental caries or dental fluorosis is prevalent.     

Passive sampling of perfluorinated acids and sulfonates using polar organic chemical integrative samplers

The applicability of a polar organic chemical integrative sampler (POCIS) for detection and determination of perfluorinated acids and sulfonates in water was studied under field conditions. Standard POCIS configurations (i.e., pharmaceutical and pesticide) were deployed in effluent from a wastewater treatment plant for 1, 2, and 3 weeks. Ten of 15 target compounds were found in POCIS, five of which were quantified in wastewater. Pest-POCIS appeared more effective for the sampling, while Pharm-POCIS had a more rapid uptake kinetic, which leads to faster saturation or equilibrium. The results showed that the pesticide configuration is probably more suitable for the sampling of this class of compounds. Based on average concentration in water over the sampling period and amount of compound adsorbed in the POCIS, we calculated sampling rates for five studied compounds and obtained values of 0.034 to 0.222 L?day^?1.     

Assessment of trace metal concentration in feathers of seabird (Larus dominicanus) sampled in the Florianópolis, SC, Brazilian coast

Cd, Co, Cr, Cu, Mn, Ni, Zn, and Pb were measured in feather samples of adult, subadult, and juvenile of Larus dominicanus, sampled in the Florianólis, SC, in the south of Brazil in December 2005, by flame atomic absorption spectrophotometry. The average of the distribution of Cd concentration in adult feathers (0.072 μg g^???1) was significantly different than that found in juvenile feathers (0.021 μg g^???1). Cu concentration averages were not significantly different between adults (13.30 μg g^???1), subadults (9.67 μg g^???1), and juveniles (13.76 μg g^???1). For adults and juveniles there was significant difference in feather concentrations for Cd, Co, Cr, Ni, and Pb. The distribution of Mn concentration averages in feathers differs between adults (11.36 μg g^???1) and juveniles (1.184 μg g^???1). Ni concentration averages of adults (5.92 μg g^???1) were significantly higher than those of juveniles (2.23 μg g^???1). For Pb, concentration averages were significantly higher in adults (7.53 μg g^???1) than in juveniles (1.47 μg g^???1). The concentration of Co and Cr in juvenile and subadults are statistically different when compared with the adults. In the present study, levels of Cd, Co, Cr, Mn, Ni, Zn, and Pb increased with age. The concentrations of essential trace elements in L. dominicanus were generally comparable to values reported in other studies. With non-essential metals (Cd, Pb, and Ni), in our study, L. dominicanus had lower values than those reported for their northern Atlantic counterparts.     

Removal of 4-chlorobenzoic acid from spiked hydroponic solution by willow trees (<Emphasis Type="Italic">Salix viminalis</Emphasis>)

Background  

Chlorobenzoic acids (CBA) are intermediate products of the aerobic microbial degradation of PCB and several pesticides. This study explores the feasibility of using basket willows, Salix viminalis, to remove 4-CBA from polluted sites, which also might stimulate PCB degradation.     

Process safety challenges for SMEs in China

While process safety regulations and standards have been in place in western countries for more than two decades, China has only recently started to officially embrace these issues with the adoption of its Process Safety Management (PSM) regulation AQ/T 3034-2010 (SAWS, 2010). However, compliance with this regulatory framework requires substantial resources and may therefore appear too complex to be efficiently implemented by small and medium sized enterprises (SMEs) in the chemical sector. This is of particular relevance as about 99% of chemical companies in China are SMEs, accounting for more than 80% of all chemical accidents. To address this issue, additional local regulations and planning activities related to process safety have been implemented in China, including the establishment of hundreds of chemical industry parks. Some of the process safety problems faced by chemical industry parks are identified and discussed in this paper. To help solve these problems, UNEP's “Responsible Production approach for Chemical Hazards Management along the Value-Chain” is introduced in this paper and suggested as a simplified PSM approach targeted specifically at SMEs which, regardless of handling hazardous chemicals in their daily operations, may not have the knowledge or capacity to efficiently implement PSM and may not fall in the scope of the PSM regulation AQ/T 3034-2010. By introducing PSM to SMEs in a more manageable way, relevant steps can be progressively implemented by companies towards full compliance with the current regulatory framework, contributing to increased safety in chemical industry parks in China.