Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Current and future solid waste management system in Northern Viet Nam with focus on Ha Noi: climate change effects and landfill management

The contribution investigates the solid waste management system in Ha Noi under consideration of the interrelation between climate change effects and landfill management by means of a cause-and-effect-analysis as well as water balances using the HELP 3.95 model and gas emission data, followed by a Strength, Weakness, Opportunities, Threats (SWOT) analysis. Even landfills are sources of methane (CH₄) emissions they are also impacted by climate change. The main effects on landfill sites are the change of climatic conditions, namely the regional water balance, extreme precipitation and storm events. The results of the water balance model results show that a geomembrane surface sealing can reduce the leachate formation significantly, a fact that is also valid for the climate change scenario with higher precipitation. The risk of flooding and erosion at the landfill sites increases, which will require a customized water management. In parallel landfill gas offers the opportunity for recovery of Greenhouse Gases (GHG) and the generation of renewable energy. Some further management options are wind turbines, photovoltaic systems or biomass for biogas conversion, which was grown on closed landfill sites. The inclusion of climate friendly management options of closed landfills in a “Good Landfill Aftercare Practice” is recommended.     

Influence of operating conditions on nitrous oxide formation during nitritation and nitrification

Nitrous oxide (N₂O), a strong greenhouse gas, can be produced by ammonium-oxidizing bacteria (AOB) as a by-product of ammonium oxidation and can potentially be formed in all types of nitrification processes. However, partial nitritation has been reported to cause significantly higher N₂O emissions than complete nitrification. In the study presented here, the mechanisms and factors that drive N₂O formation by AOB were investigated with respect to different operational strategies to achieve nitrite accumulation base on combined evaluation of oxygen uptake rate (OUR) and N₂O formation rate. On the one hand, N₂O formation during partial nitritation and nitrification in a continuously stirred tank reactor (CSTR) with continuous aerobic conditions was observed. On the other hand, the effect of intermittent aeration on N₂O formation during nitrification was investigated. The presence of nitrite, the extend of sludge-specific ammonium loading, low oxygen concentration, and transition from aerobic to anoxic conditions significantly increased N₂O formation in this reactor independently from each other, indicating that different formation pathways, supposedly via nitrite or hydroxylamine, were active.     

Impact of temperature on the dynamics of organic matter and on the soil-to-plant transfer of Cd,Zn and Pb in a contaminated agricultural soil

Predicting the soil-to-plant transfer of metals in the context of global warming has become a major issue for food safety. It requires a better understanding of how the temperature alters the bioavailability of metals in cultivated soils. This study focuses on one agricultural soil contaminated by Cd, Zn and Pb. DGT measurements were performed at 10, 20 and 30 °C to assess how the bioavailability of metals was affected by a rise in soil temperature. A lettuce crop was cultivated in the same conditions to determine if the soil-to-plant transfer of metals increased with a rise in soil temperature. A gradual decline in Cd and Zn bioavailability was observed from 10 to 30 °C, which was attributed to more intense complexation of metals in the pore water at higher temperatures. Together with its aromaticity, the affinity of dissolved organic matter (DOM) for metals was indeed suspected to increase with soil temperature. One main output of the present work is a model which satisfactorily explains the thermal-induced changes in the characteristics of DOM reported in Cornu et al. (Geoderma 162:65–70, 2011) by assuming that the mineralization of initial aliphatic compounds followed a first-order reaction, increased with soil temperature according to the Arrhenius law, and due to a priming effect, led to the appearance of aromatic molecules. The soil-to-plant transfer of Cd and Zn was promoted at higher soil temperatures despite a parallel decrease in Cd and Zn bioavailability. This suggests that plant processes affect the soil-to-plant transfer of Cd and Zn the most when the soil temperature rises.     

Growth dynamics of Chinese wingnut (Pterocarya stenoptera) seedlings and its effects on soil chemical properties under simulated water change in the Three Gorges Reservoir Region of Yangtze River

Pterocarya stenoptera is a native deciduous tree species and a candidate for reforestation in the riparian zones of the Three Gorges Reservoir Region of Yangtze River in China. Water treatments of continuous flooding (CF) and periodic flooding–drought (PF) were applied to examine the growth dynamics of 4-month-old P. stenoptera seedlings and its effects on soil chemical properties. Results showed that P. stenoptera seedlings in both CF and PF significantly decreased leaf biomass accumulation and the height and diameter growth as compared to that in control (CK; treatment with well-watered, well-drained soil), respectively. There was no significant difference in stem biomass among the three groups, but root biomass in PF showed severe reduction compared to that in both CK and CF. Total biomass in PF was significantly decreased compared to that in CK, but comparable to that in CF. Furthermore, no significant difference was found between CF and CK in total biomass. Water treatments in the unplanted soil pots significantly influenced soil pH, soil organic matter (OM), total nitrogen (TN), and alkali hydrolysable nitrogen (AN) contents, in contrast to no significant effects in total phosphorus (TP), total potassium (TK), available phosphorus (AP), and available potassium (AK) contents. In P. stenoptera soils, there were significant effects by water treatment, time, and treatment × time in the eight tested soil chemical properties, except treatment in TK and time effect in OM content. Compared to unplanted soils, the growth of P. stenoptera seedlings significantly increased soil pH value and OM, TN, TP, and TK contents, while decreasing AN, AP, and AK contents in CK group, augmented the mean value of each of the tested soil chemical properties with an exception of AK content in CF group, and increased soil pH value and TN, AN, TP, and AP contents with no significant differences in OM, TK, and AK contents in PF group. Given the fact that TN and TP contents significantly increased in P. stenoptera soils as compared to those in unplanted soils, growth of P. stenoptera seedlings should be a successful candidate for restoration within the highly dynamic hydrologic zone of the riparian zones of the Three Gorges Reservoir Region.     

Engineering,Operation and Maintenance of Electrostatic Precipitators on Open Hearth Furnaces

The photochemical reaction of various olefins and nitrogen dioxide was studied under conditions of controlled temperature, pressure, and humidity in a 200 liter stirred glass reactor. The hydrocarbon concentration in the reactor during four and five hour irradiation periods was monitored with a flame ionization chromatograph. Reaction rate constants, based on three consecutive first order reactions, were calculated for reactor temperatures of 20, 25, 30, and 35 degrees centigrade. Activation energies for the three consecutive reactions were calculated from the Arrhenius equation. Branched and straight chain olefins were studied at initial concentrations of 5.0 to 10.0 parts per million.s     

Ectomised conductors in the golden orb-web spider, Nephila plumipes (Araneoidea): a male adaptation to sexual conflict?

Male genitalia may facilitate sperm protection by acting as a plug that prevents or hinders future matings. The pedipalps (intromittant organs) of males of the orb-web spider, Nephila plumipes, have a conductor with a peculiarly curved ending and a triangular process near the terminal end. The tip of the conductor, including the process, breaks during most matings and remains inside the female genital tract. We explored the possible function of the conductor as a mating plug using the double-mating sterile-male technique. Our data are not consistent with a plug function because males use only one pedipalp in each mating, thus leaving an unobstructed insemination duct available for future matings; conductors of males mating with virgin females are not more likely to break than those of males mating with mated females, and second males show no preference for used or unused spermathecae. In addition, males that inserted their palp in the insemination duct that contained a tip of the conductor from a previous male obtained a share in the paternity of the female's clutch of eggs. Interestingly, the conductor is more likely to break if it is inserted in an unused spermatheca. We argue that several lines of evidence suggest that the conductor breaks as a result of intersexual conflict over the duration of copulation.     

Integral assessment of estrogenic potentials in sediment-associated samples

Background, aim, and scope  The enzyme-linked receptor assay (ELRA) detects estrogenic and anti-estrogenic effects at the molecular level of receptor binding and is a useful tool for the integrative assessment of ecotoxicological potentials caused by hormonally active agents (HAA) and endocrine disrupting compounds (EDC). The main advantage of the ELRA is its high sample throughput and its robustness against cytotoxicity and microbial contamination. After a methodological adaptation to salinity of the ELRA, according to the first part of this study, which increased its salinity tolerance and sensitivity for 17-β-estradiol, the optimised ELRA was used to investigate 13 native sediments characterised by different levels of salinity and chemical contamination. The applicability of the ELRA for routine analysis in environmental assessment was evaluated. Salinity is often a critical factor for bioassays in ecotoxicological sediment assessment. Therefore, salinity of the samples was additionally adjusted to different levels to characterise its influence on elution and binding processes of receptor-binding substances. Materials and methods  The ELRA was carried out with the human estrogen receptor α (ER) in a 96-well microplate format using the experimental setup known from the competitive immunoassay based on ligand–protein interaction. It is an important improvement that a physiologically relevant receptor was used as a linking protein instead of an antibody. The microplates were coated with a 17-β-estradiol-BSA conjugate, and dilution series of estradiol and of native sediment samples were added and incubated with the ER. After a washing step, a biotinylated mouse anti-ER antibody was added to each well. Receptor binding to estradiol, agonistic and antagonistic receptor binding, were determined by a streptavidin-POD-biotin complex with subsequent measurement of the peroxidase activity at the wavelength of 450 nm using a commercial ELISA multiplate reader. The sediment elutriates and pore water samples of sediments were tested in a dilution series to evaluate at which dilution step the receptor-binding potential ends. In the elution process (see Section 2.1 to 2.2), a method was developed to adjust the salinity to the levels of the reference testings, which offers an appropriate option to adjust the salinity in both directions. Statistical evaluation was made with a combination of the Mann–Whitney U test and the pT-method. Results  This part of the study characterised the environmental factor ‘salinity’ for prospective applications of the ELRA. Using reference substances such as 17-β-estradiol, the ELRA showed sigmoid concentration-effect relations over a broad range from 0.05 μg/l to 100 μg/l under physiological conditions. After methodological optimisation, both sensitivity and tolerance of the assay against salinity could be significantly raised, and the ELRA became applicable under salinity conditions up to concentrations of 20.5‰. The mean relative inter-test error (n = 3) was around 11% with reference substances and below 5% for single sediments elutriates in three replicates each. For sediment testings, the pore water and different salinity-adjusted elutriates of 13 sediments were used. A clear differentiation of the receptor-binding potential could be reached by application of the pT-method. Thereby, pT-values from one to six could be assigned to the sediments, and the deviation caused by the different salinity conditions was one pT-value. The mean standard deviation in the salinity adaptation procedure of the elutriates was below 5%. Discussion  Although the ELRA has already been used for assessments of wastewater, sludge and soil, its applicability for samples to different salinity levels has not been investigated so far. Even if the ELRA is not as sensitive as the E-screen or the YES-assay, with regard to reference substances like 17-β-estradiol, it is a very useful tool for pre-screening, because it is able to integrate both estrogenic as well as anti-estrogenic receptor-binding effects. According to the results of sediment testing, and given the integrative power to detect different directions of effects, the ELRA shows sufficient sensitivity and salinity tolerance to discriminate receptor-binding potentials in environmental samples. Conclusions  The optimised ELRA assay is a fast, cost-effective, reliable and highly reproducible tool that can be used for high-throughput screening in a microplate format in detecting both estrogenic and anti-estrogenic effects. Additionally, the ELRA is robust against microbial contaminations, and is not susceptible towards cytotoxic interferences like the common cell-culture methods. The general applicability and sufficient sensitivity of the ELRA was shown in freshwater environments. Marine and brackish samples can be measured up to salinity levels of 20.5‰. Recommendations and perspectives  In view of the proven sensitivity, functionality and the fastness of the ELRA, it is recommendable to standardise the test method. At the moment, no adequate in vitro test procedure exists which is standardised to DIN or ISO levels. The E-screen and the yeast estrogen/androgen screens (YES/YAS) sometimes underlie strong cytotoxic effects, as reported in the first part of this study. Further development of an ELRA assay using human androgen receptors appears to be very promising to gain information about androgenic and anti-androgenic effects, too. This would offer a possibility to use the ELRA as a fast and reliable pre-screening tool for the detection of endocrine potentials, thus minimising time and cost-expensive animal experiments.