Factors affecting nitrate distribution in shallow groundwater under a beef farm in South Eastern Ireland

Groundwater contamination was characterised using a methodology which combines shallow groundwater geochemistry data from 17 piezometers over a 2 yr period in a statistical framework and hydrogeological techniques. Nitrate–N (NO₃-N) contaminant mass flux was calculated across three control planes (rows of piezometers) in six isolated plots. Results showed natural attenuation occurs on site although the method does not directly differentiate between dilution and denitrification. It was further investigated whether NO₃-N concentration in shallow groundwater (<5 m below ground level) generated from an agricultural point source on a 4.2 ha site on a beef farm in SE Ireland could be predicted from saturated hydraulic conductivity (K_sat) measurements, ground elevation (m Above Ordnance Datum), elevation of groundwater sampling (screen opening interval) (m AOD) and distance from a dirty water point pollution source. Tobit regression, using a background concentration threshold of 2.6 mg NO₃-N L⁻¹ showed, when assessed individually in a step wise procedure, K_sat was significantly related to groundwater NO₃-N concentration. Distance of the point dirty water pollution source becomes significant when included with K_sat in the model. The model relationships show areas with higher K_sat values have less time for denitrification to occur, whereas lower K_sat values allow denitrification to occur. Areas with higher permeability transport greater NO₃-N fluxes to ground and surface waters. When the distribution of Cl⁻ was examined by the model, K_sat and ground elevation had the most explanatory power but K_sat was not significant pointing to dilution having an effect. Areas with low NO₃ concentration and unaffected Cl⁻ concentration points to denitrification, low NO₃ concentration and low Cl⁻ chloride concentration points to dilution and combining these findings allows areas of denitrification and dilution to be inferred. The effect of denitrification is further supported as mean groundwater NO₃-N was significantly (P < 0.05) related to groundwater N₂/Ar ratio, redox potential (Eh), dissolved O₂ and N₂ and was close to being significant with N₂O (P = 0.08). Calculating contaminant mass flux across more than one control plane is a useful tool to monitor natural attenuation. This tool allows the identification of hot spot areas where intervention other than natural attenuation may be needed to protect receptors.     

测定地表水及饮用水中硫酸盐的两种方法探讨

通过比较两种监测分析方法,分析了测定硫酸盐分光光度法的影响因素、存在问题,以及火焰原子吸收法的优点,提出对不同浓度范围的硫酸盐,宜采用合适的分析方法,以减小测定的误差,提高测定结果的准确性和科学性。     

Spatial distribution of U isotopes in sea-water sediments, Red Sea, Egypt

Isotopes of uranium in the sea-water sediments collected from two different areas (El Hamraween harbour and Ras El Behar) on the Egyptian coast of the red sea have been studied using radiochemical separation procedures and alpha-particle spectrometry. Activity concentrations of ²³⁸U, ²³⁵U, ²³⁴U were calculated. The activities observed indicated enhanced radioactivity levels in sea-water sediments of El Hamraween harbour area due to the activities of phosphate shipment operation. Secular equilibrium between ²³⁴U and ²³⁸U was found in the analyzed samples. The average activity ratio of ²³⁵U/²³⁸U was close to the value 0.046 for uranium in nature.     

Microdistribution of Am in structures of submerged macrophyte Elodea canadensis growing in the Yenisei River

A submerged macrophyte of the Yenisei River, Elodea canadensis, was used to study the microdistribution of the artificial radionuclide ²⁴¹Am among different components of the plant. The total amount of ²⁴¹Am added to the experimental system was 1850 ± 31 Bq/L. The total amount of ²⁴¹Am accumulated by the plants was 182 Bq per sample, or 758,333 ± 385 Bq/kg dry mass. It has been found that the major portion of ²⁴¹Am accumulated by E. canadensis, up to 85%, was bound to solid components of the cells. It is observed that the microdistribution of ²⁴¹Am within different components of the submerged plant E. canadensis was not uniform. ²⁴¹Am distribution vary depending on the age of the leaf blades, the state of the cells and morphological features of the plant stem.     

Validation of reliable and selective methods for direct determination of glyphosate and aminomethylphosphonic acid in milk and urine using LC-MS/MS

Simple high-throughput procedures were developed for the direct analysis of glyphosate [N-(phosphonomethyl)glycine] and aminomethylphosphonic acid (AMPA) in human and bovine milk and human urine matrices. Samples were extracted with an acidified aqueous solution on a high-speed shaker. Stable isotope labeled internal standards were added with the extraction solvent to ensure accurate tracking and quantitation. An additional cleanup procedure using partitioning with methylene chloride was required for milk matrices to minimize the presence of matrix components that can impact the longevity of the analytical column. Both analytes were analyzed directly, without derivatization, by liquid chromatography tandem mass spectrometry using two separate precursor-to-product transitions that ensure and confirm the accuracy of the measured results. Method performance was evaluated during validation through a series of assessments that included linearity, accuracy, precision, selectivity, ionization effects and carryover. Limits of quantitation (LOQ) were determined to be 0.1 and 10 µg/L (ppb) for urine and milk, respectively, for both glyphosate and AMPA. Mean recoveries for all matrices were within 89–107% at three separate fortification levels including the LOQ. Precision for replicates was ≤7.4% relative standard deviation (RSD) for milk and ≤11.4% RSD for urine across all fortification levels. All human and bovine milk samples used for selectivity and ionization effects assessments were free of any detectable levels of glyphosate and AMPA. Some of the human urine samples contained trace levels of glyphosate and AMPA, which were background subtracted for accuracy assessments. Ionization effects testing showed no significant biases from the matrix. A successful independent external validation was conducted using the more complicated milk matrices to demonstrate method transferability.     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

Serum concentrations of persistent organic pollutants (POPs) in the inhabitants of a Sicilian city

Background

Polychlorinated biphenyls (PCBs) and organochlorine pesticides are common environmental contaminants that have been associated with human health problems.

Objectives

To assess serum concentrations of several organochlorine contaminants in general population living in a city with an ancient agricultural tradition and to identify possible exposure sources in Sicily.

Methods

A cross-sectional study was conducted on 101 individuals. Each participant answered a face-to-face questionnaire submitted by well-trained personnel and provided a serum sample which was analyzed for the concentrations of PCBs, HCB, HCHs and DDTs by using gas-chromatography coupled with mass spectrometry.

Results

HCB, p,p′-DDE, PCB 138, PCB 153 and PCB 180 were detected in more than 80% of the study participants. The ng g⁻¹ lipid median concentrations were: 18.6 for HCB; 175.1 for p,p′-DDE; 22. for PCB 138; 32.5 for PCB 153 and 23.0 for PCB 180. PCB 153 and PCB 138, PCB 138 and PCB 180, PCB 153 and PCB 180, and p,p′-DDE and HCB showed a high correlation each other (p < 0.05). HCB and p,p′-DDE concentrations were significantly higher in subjects >49 years old (adj-p = 0.03 in 50-69 years old and adj-p < 0.001 in >69 years old, respectively) whereas PCB 138, PCB 153 and PCB 180 concentrations were higher in males (adj-p = 0.03), in subjects >69 years old (adj-p = 0.04) and in current smokers (adj-p = 0.04).

Conclusions

The present study shows that serum concentrations of organochlorine compounds detected in subjects living in a small Sicilian city with ancient agricultural tradition are similar to those found in subjects living in urban areas of other countries. However, further investigations are needed to compare data from rural/urban areas in the same country, assessing correlations between serum concentrations of several chemical compounds and potential health effects in general population.     

4种重金属离子对间接火焰原子吸收光谱法测定铝的干扰

空气-乙炔间接火焰原子吸收法是我国目前运用较多且易于推广的铝检测方法,研究了Mg2+、Ca2+、Zn2+和Ni2+4种离子对此法测定0.40 mg/L Al3+的干扰情况。得出如下结论:(1)在±5%误差范围内,15.10 mg/L Mg2+、105.00mg/L Ca2+、0.23 mg/L Zn2+、0.88 mg/L Ni2+对0.40 mg/L Al3+无干扰。(2)本方法虽然操作复杂,但成本较低、灵敏度高,检测的浓度范围宽、稳定性好,加标回收率为96%~99%,检出限为0.04 mg/L,适宜测定范围为0.05~100.00 mg/L,适用于饮用水、河水及地下水中Al3+的测定。     

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in seven different marine bird species from Iceland

Data on distribution, concentration and trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) is scarce in biota from the sub-Arctic region of the Atlantic. The present study is an investigation on PBDE and HBCD concentrations in eggs from seven marine bird species from Iceland, i.e. common eider (Somateria mollissima), arctic tern (Sterna paradisaea), guillemot (Uria aalge), fulmar (Fulmarus glacialis), lesser black-backed gull (Larus fuscus), great black-backed gull (Larus marinus) and great skua (Stercorarius skua). Concentrations of sum PBDEs ranged from 44 ng g⁻¹ fat in eider eggs to 2400 ng g⁻¹ fat in great skua eggs. The contribution of different PBDE congeners to the sum concentration differed between species. Concentration of HBCDs (sum of α−,β⁻ and γ−HBCD) ranged from 1.3 ng g⁻¹ fat in arctic tern eggs to 41 ng g⁻¹ fat in great black-backed gull. PCA on PBDE and HBCD shows different trends between the two BFR groups, further indicating different sources/usage. Investigations on any potential health or population effects of environmental pollutants on the great skua are advised since both the PBDE and HBCD concentrations are high.     

Application of indoxacarb for managing shoot and fruit borer of eggplant (Solanum melongena L.) and its decontamination

Indoxacarb was applied at 75 and 150 g a.i. ha^{? 1} for two years to an eggplant (Solanum melongena L.) crop grown in the field plots in order to evaluate its efficacy for management of the lepidopteron pest, shoot and fruit borer. The residues of the insecticide were quantified by high-pressure liquid chromatography (HPLC). The mean initial deposits of indoxacarb on eggplant fruits were found to be 2.60–2.634 mg kg^{? 1} and 3.64–3.68 mg kg^{? 1} from the two rates of applications, respectively. They declined with time and reached to non-detectable (< 0.02 mg kg^{? 1}) after 15–20 d. Residues dissipated with a half-life of 3.0–3.8 d from both first and second-year application. A 3 d waiting period for harvest of fruits after insecticide application and processing resulted in the residue levels that were below the Codex maximum residue limit (MRL) of 0.5 mg kg^{? 1} thereby achieving a maximum safety and minimum risk to consumers. The best combination of chemicals for decontamination of indoxacarb was found to be by washing with a mixture of alkali and potassium permanganate (KMnO₄) thereby resulting in the removal of 67.5% and 59.2 % residues for 5 and 10 μ g g^{? 1} spiking doses, respectively. Major products formed on reaction of indoxacarb with alkali were identified by electron spray ionization chromatography/mass spectrometry (ESI/MS). The per cent reduction on the weight and number basis of treated eggplant plots were compared to those observed in control plots to demonstrate the effectiveness of indoxacarb treatment on shoot and fruit borer population.