Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.     

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Photodegradation of sulfonamides and their N 4-acetylated metabolites in water by simulated sunlight irradiation: kinetics and identification of photoproducts

Once released into the aquatic environment, pharmaceuticals may undergo different degradation processes. Photodegradation, for example, might be an important elimination process for light-sensitive pharmaceuticals, such as antibiotics. In this study, the fate of sulfonamides (sulfamethazine, sulfadiazine, and sulfamethoxazole) and their N ⁴-acetylated metabolites (N ⁴-acetylsulfadiazine, N ⁴-acetylsulfamethazine, and N ⁴-acetylsulfamethoxazole) under simulated sunlight irradiation was investigated. The irradiation resulted in total or almost total degradation (88 to 98 %) of the pharmaceuticals tested, except for sulfamethazine (52 %), during 24 h of irradiation. The photoproducts of all investigated pharmaceuticals have been analyzed using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Structure elucidation performed from photodegradation products of both, sulfonamides and their N ⁴-acetylated metabolites, clearly showed two major formation pathways. These were cleavage of the sulfonamide bond as well as SO₂ extrusion. In total, nine photoproducts were elucidated. Among these photoproducts, the tautomers of sulfamethoxazole and desulfonated products of sulfadiazine and sulfamethazine were also present. Tautomers of sulfadiazine and sulfamethazine have been characterized here for the first time as well as some photoproducts of sulfadiazine, sulfametoxazole, and their metabolites N ⁴-acetylsulfadiazine and N ⁴-acetylsulfametoxazole. The obtained results are an important piece in the complex puzzle for assessing the environmental fate of sulfonamides and their metabolites in the environment.     

Activated sludge systems removal efficiency of veterinary pharmaceuticals from slaughterhouse wastewater

The knowledge on the efficiency of wastewater treatment plants (WWTPs) from animal food production industry for the removal of both hormones and antibiotics of veterinary application is still very limited. These compounds have already been reported in different environmental compartments at levels that could have potential impacts on the ecosystems. This work aimed to evaluate the role of activated sludge in the removal of commonly used veterinary drugs, enrofloxacin (ENR), tetracycline (TET), and ceftiofur, from wastewater during a conventional treatment process. For that, a series of laboratory-controlled experiments using activated sludge were carried out in batch reactors. Sludge reactors with 100 μg/L initial drug charge presented removal rates of 68 % for ENR and 77 % for TET from the aqueous phase. Results indicated that sorption to sludge and to the wastewater organic matter was responsible for a significant percentage of drugs removal. Nevertheless, these removal rates still result in considerable concentrations in the aqueous phase that will pass through the WWTP to the receiving environment. Measuring only the dissolved fraction of pharmaceuticals in the WWTP effluents may underestimate the loading and risks to the aquatic environment.     

Long Range Cloud Diffusion in the Lower Atmosphere

Previous attempts to measure heavy metals in air are discussed with particular reference to lead. A polarographic method was developed for lead in air samples taken on glass fiber sheet. Using this method, the distribution of lead across the glass fiber sheet was investigated, and within experimental error, found to be uniform. Air samples from 18 Ontario cities, previously analyzed for benzo [a]pyrene content were analyzed.     

Comprehensive Area Surveys in New York State

The proposed By-law changes have been suggested over the last two years. They are basically housekeeping changes which correct the language, eliminate duplications, and clarify the dates for the receipt and acceptance of the ballots for nominees for the Board. The major revision proposed is in Article XV of the Technical Council which was necessitated by the new structure of the Technical Council approved by the Board of Directors in June 1970.     

重庆市大气污染对锌材料腐蚀的经济损失分析

简要介绍了材料大气腐蚀经济损失的估算方法,并以2002年为基准年,选择了重庆市主城中心的6个功能区作为代表性区域,运用腐蚀破坏剂量响应函数和使用寿命计算公式对锌材料的腐蚀经济损失进行了定量估算.结果表明,由大气污染腐蚀破坏锌材料造成的年直接经济损失约为4061.7万元,约为同期GDP的0.1%.其中,干沉降对经济损失总量的贡献率在71%～99%之间,均值为92%.     

Effect of liquid swine manure rate, incorporation, and timing of rainfall on phosphorus loss with surface runoff

Excessive manure phosphorus (P) application increases risk of P loss from fields. This study assessed total runoff P (TPR), bioavailable P (BAP), and dissolved reactive P (DRP) concentrations and loads in surface runoff after liquid swine (Sus scrofa domesticus) manure application with or without incorporation into soil and different timing of rainfall. Four replicated manure P treatments were applied in 2002 and in 2003 to two Iowa soils testing low in P managed with corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] rotations. Total P applied each time was 0 to 80 kg P ha(-1) at one site and 0 to 108 kg P ha(-1) at the other. Simulated rainfall was applied within 24 h of P application or after 10 to 16 d and 5 to 6 mo. Nonincorporated manure P increased DRP, BAP, and TPR concentrations and loads linearly or exponentially for 24-h and 10- to 16-d runoff events. On average for the 24-h events, DRP, BAP, and TPR concentrations were 5.4, 4.7, and 2.2 times higher, respectively, for nonincorporated manure than for incorporated manure; P loads were 3.8, 7.7, and 3.6 times higher; and DRP and BAP concentrations were 54% of TPR for nonincorporated manure and 22 to 25% for incorporated manure. A 10- to 16-d rainfall delay resulted in DRP, BAP, and TPR concentrations that were 3.1, 2.7, and 1.1 times lower, respectively, than for 24-h events across all nonincorporated P rates, sites, and years, whereas runoff P loads were 3.8, 3.6, and 1.6 times lower, respectively. A 5- to 6-mo simulated rainfall delay reduced runoff P to levels similar to control plots. Incorporating swine manure when the probability of immediate rainfall is high reduces the risk of P loss in surface runoff; however, this benefit sharply decreases with time.