Identification of new ozonation disinfection byproducts of 17β-estradiol and estrone in water

Estrogens are a class of micro-pollutants found in water at low concentrations (in the ng L⁻¹ range), but often sufficient to exert estrogenic effects due to their high estrogenic potency. Disinfection of waters containing estrogens through oxidative processes has been shown to lead to the formation of disinfection byproducts, which may also be estrogenic. The present work investigates the formation of disinfection byproducts of 17β-estradiol (E2) and estrone (E1) in the treatment of water with ozone. Experiments have been carried out at two different concentrations of the estrogens in ground water (100 ng L⁻¹ and 100 μg L⁻¹) and at varying ozone dosages (0-30 mg L⁻¹). Detection of the estrogens and their disinfection byproducts in the water samples has been performed by means of ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a triple quadrupole (QqQ) and a quadrupole-time of flight (QqTOF) instrument. Both E2 and E1 have been found to form two main byproducts, with molecular mass (MM) 288 and 278 in the case of E2, and 286 and 276 in the case of E1, following presumably the same reaction pathways. The E2 byproduct with MM 288 has been identified as 10epsilon-17beta-dihydroxy-1,4-estradieno-3-one (DEO), in agreement with previously published results. The molecular structures and the formation pathways of the other three newly identified byproducts have been suggested. These byproducts have been found to be formed at both high and low concentrations of the estrogens and to be persistent even after application of high ozone dosages.     

Mercury, lead and cadmium in human milk in relation to diet, lifestyle habits and sociodemographic variables in Madrid (Spain)

Background

Although breastfeeding is the ideal way of nurturing infants, it can be a source of exposure to toxicants. This study reports the concentration of Hg, Pb and Cd in breast milk from a sample of women drawn from the general population of the Madrid Region, and explores the association between metal levels and socio-demographic factors, lifestyle habits, diet and environmental exposures, including tobacco smoke, exposure at home and occupational exposures.

Methods

Breast milk was obtained from 100 women (20 mL) at around the third week postpartum. Pb, Cd and Hg levels were determined using Atomic Absorption Spectrometry. Metal levels were log-transformed due to non-normal distribution. Their association with the variables collected by questionnaire was assessed using linear regression models. Separate models were fitted for Hg, Pb and Cd, using univariate linear regression in a first step. Secondly, multivariate linear regression models were adjusted introducing potential confounders specific for each metal. Finally, a test for trend was performed in order to evaluate possible dose-response relationships between metal levels and changes in variables categories.

Results

Geometric mean Hg, Pb and Cd content in milk were 0.53 μg L⁻¹, 15.56 μg L⁻¹, and 1.31 μg L⁻¹, respectively. Decreases in Hg levels in older women and in those with a previous history of pregnancies and lactations suggested clearance of this metal over lifetime, though differences were not statistically significant, probably due to limited sample size. Lead concentrations increased with greater exposure to motor vehicle traffic and higher potato consumption. Increased Cd levels were associated with type of lactation and tended to increase with tobacco smoking.

Conclusions

Surveillance for the presence of heavy metals in human milk is needed. Smoking and dietary habits are the main factors linked to heavy metal levels in breast milk. Our results reinforce the need to strengthen national food safety programs and to further promote avoidance of unhealthy behaviors such as smoking during pregnancy.     

Effects of municipal solid waste compost and mineral fertilizer amendments on soil properties and heavy metals distribution in maize plants (Zea mays L.)

Soil amendments based on crop nutrient requirements are considered a beneficial management practice. A greenhouse experiment with maize seeds (Zea mays L.) was conducted to assess the inputs of metals to agricultural land from soil amendments. Maize seeds were exposed to a municipal solid waste (MSW) compost (50 Mg ha⁻¹) and NPK fertilizer (33 g plant⁻¹) amendments considering N plant requirement until the harvesting stage with the following objectives: (1) determine the accumulation of total and available metals in soil and (2) know the uptake and ability of translocation of metals from roots to different plant parts, and their effect on biomass production. The results showed that MSW compost increased Cu, Pb and Zn in soil, while NPK fertilizer increased Cd and Ni, but decreased Hg concentration in soil. The root system acted as a barrier for Cr, Ni, Pb and Hg, so metal uptake and translocation were lower in aerial plant parts. Biomass production was significantly enhanced in both MSW and NPK fertilizer-amended soils (17%), but also provoked slight increases of metals and their bioavailability in soil. The highest metal concentrations were observed in roots, but there were no significant differences between plants growing in amended soil and the control soil. Important differences were found for aerial plant parts as regards metal accumulation, whereas metal levels in grains were negligible in all the treatments.     

Differentiation of nitrous oxide emission factors for agricultural soils

Nitrous oxide (N₂O) direct soil emissions from agriculture are often estimated using the default IPCC emission factor (EF) of 1%. However, a large variation in EFs exists due to differences in environment, crops and management. We developed an approach to determine N₂O EFs that depend on N-input sources and environmental factors. The starting point of the method was a monitoring study in which an EF of 1% was found. The conditions of this experiment were set as the reference from which the effects of 16 sources of N input, three soil types, two land-use types and annual precipitation on the N₂O EF were estimated. The derived EF inference scheme performed on average better than the default IPCC EF. The use of differentiated EFs, including different regional conditions, allows accounting for the effects of more mitigation measures and offers European countries a possibility to use a Tier 2 approach.     

Multi-decadal changes in tundra environments and ecosystems: synthesis of the International Polar Year-Back to the Future project (IPY-BTF)

Understanding the responses of tundra systems to global change has global implications. Most tundra regions lack sustained environmental monitoring and one of the only ways to document multi-decadal change is to resample historic research sites. The International Polar Year (IPY) provided a unique opportunity for such research through the Back to the Future (BTF) project (IPY project #512). This article synthesizes the results from 13 papers within this Ambio Special Issue. Abiotic changes include glacial recession in the Altai Mountains, Russia; increased snow depth and hardness, permafrost warming, and increased growing season length in sub-arctic Sweden; drying of ponds in Greenland; increased nutrient availability in Alaskan tundra ponds, and warming at most locations studied. Biotic changes ranged from relatively minor plant community change at two sites in Greenland to moderate change in the Yukon, and to dramatic increases in shrub and tree density on Herschel Island, and in subarctic Sweden. The population of geese tripled at one site in northeast Greenland where biomass in non-grazed plots doubled. A model parameterized using results from a BTF study forecasts substantial declines in all snowbeds and increases in shrub tundra on Niwot Ridge, Colorado over the next century. In general, results support and provide improved capacities for validating experimental manipulation, remote sensing, and modeling studies.     

Dietary exposure of rainbow trout to 8:2 and 10:2 fluorotelomer alcohols and perfluorooctanesulfonamide: Uptake, transformation and elimination

The bioaccumulation of perfluorooctanesulfonamide (PFOSA) and two fluorotelomer alcohols (8:2 FTOH, 10:2 FTOH) by rainbow trout (Oncorhynchus mykiss) through dietary exposure, including depuration rates and metabolism was investigated. Concentrations in the spiked feed ranged from 10.9 μg g⁻¹ wet weight (wet wt) for PFOSA and 6.7 μg g⁻¹ wet wt for 8:2 FTOH to 5.0 μg g⁻¹ wet wt for 10:2 FTOH. Trout was fed at 1.5% body weight per day for 30 d and depuration was followed for up to 30 d following previously published dietary exposure protocols. Perfluorooctanesulfonate (PFOS) was the major perfluoroalkylsulfonate (PFSA) detected in fish following dietary exposure to PFOSA. Half-lives of PFOS and PFOSA were 16.9 ± 2.5 and 6.0 ± 0.4 d, respectively. A biomagnification factor (BMF) of 0.023 was calculated for PFOSA which indicates that dietary exposure to PFOSA does not result in biomagnification in the rainbow trout. PFOS had a BMF of 0.08. The fluorotelomer saturated acids (8:2 FTCA, 10:2 FTCA) and fluorotelomer unsaturated acids (8:2 FTUCA, 10:2 FTUCA) were the major products detected in rainbow trout following dietary exposure to 8:2 FTOH and 10:2 FTOH, respectively. Half-lives were 3.7 ± 0.4, 2.1 ± 0.5, 3.3, and 1.3 d for 10:2 FTCA, 10:2 FTUCA, 8:2 FTCA, and 8:2 FTUCA, respectively. Small amounts of perfluorooctanoate (PFOA) and perfluorodecanoate (PFDA) were also detected in the FTOH exposed fish.     

Concentrations and sources of Dechlorane Plus in sewage sludge

Sewage sludge from 31 urban Spanish wastewater treatment plants (WWTP) was analyzed for the emerging halogenated flame retardant Dechlorane Plus (DP). Concentrations of the two major isomers in the technical mixture, syn and anti, ranged between 0.903-19.2 and 1.55-75.1 ng g⁻¹ dry weight, respectively. Overall, concentrations of DP were lower than those of polybrominated diphenyl ethers (PBDEs) (9.10-995 ng g⁻¹ dry weight) and this is likely related to the higher usage of brominated flame retardants. The average ratio of the syn isomer to total DP (f_syn) was 0.28 ± 0.05, which is similar to that of the commercial mixture. Comparing different wastewater treatment methods, we found lower concentrations in those using biological nitrogen and phosphorous elimination, suggesting that DP is susceptible to microbial degradation and that anti-DP is more so, given the enrichment of syn-DP in the sewage sludge. Principal components analysis revealed significant positive correlation (r = 0.619, p < 0.05) between total DP concentrations with the contribution of industrial input to waste streams. This implies release of DP is related to industrial activity, likely stemming from the use of the technical product during manufacture of consumer goods. However, use and disposal of products containing DP could not be dismissed. According to our knowledge, this is the first report on DP in WWTP sludge.     

Transfer functions for solid-solution partitioning of cadmium for Australian soils

To assess transport and ecotoxicological risks of metals, such as cadmium (Cd) in soils, models are needed for partitioning and speciation. We derived regression-based “partition-relations” based on adsorption and desorption experiments for main Australian soil types. First, batch adsorption experiments were carried out over a realistic range of dissolved Cd concentrations in agricultural soils in Australia. Results showed linear sorption relationships, implying the adequacy of using Kd values to describe partitioning. Desorption measurements were then carried out to assess in-situ Kd values and relate these to soil properties The best transfer functions for solid-solution partitioning were found for Kd values relating total dissolved Cd concentration to total soil Cd concentrations, accounting for the variation in pH, SOM contents and DOC concentrations. Model predictions compared well with measurements of an independent data set, but there was a tendency to underestimate dissolved Cd concentrations of highly polluted soils.     

Occupational exposure to formaldehyde in an institute of morphology in Brazil: a comparison of area and personal sampling

Background, aims, and scope

Formaldehyde (FA) is a harmful chemical, which is classified as carcinogenic to humans (Group 1) by the International Agency for Research on Cancer. Solutions of FA that are used to preserve cadavers in research and education morphological institutes represent a risk to occupational health of professionals and students. During the dissection of cadavers in the anatomy laboratories, FA vapors are emitted, resulting in the exposure of students and their instructors to elevated levels of FA. The World Health Organization recommends an air quality guideline value of 0.1 mg m^?3 for exposure to FA. The limit of occupational exposure adopted by the Brazilian legislation (2.3 mg m^?3) is markedly higher than those adopted by institutions of other countries around the world. The purpose of this study was to determine the levels of personal exposure and the area concentration of FA in the morphology department of the Federal Fluminense University, Brazil, and investigate and compare the relationship between them.

Methods

Four rooms distributed in the three floors of the Morphology Department were evaluated: the embalming laboratory, the anatomy laboratories, the corridor of the teachers?? rooms, and the entrance hall. Thirty-six samples in total were collected in the second semester of 2010 and first semester of 2011. The air sampling and FA analysis were performed according to the EPA TO-11A Protocol, using a diffusive sampling device for carbonyl compounds. Personal samples were collected from monitors using a sampling device pinned on each person??s lapel. The samples were analyzed using rapid resolution liquid chromatography with UV-DAD detection at 360 nm.

Results and discussion

The concentrations of FA ranged from 0.20 and 0.18 mg m^?3 in the corridor between the teachers?? rooms, 0.03 to 0.37 mg m^?3 in the entrance hall, 0.22 to 2.07 mg m^?3 in the anatomy laboratory, 2.21 to 2.52 mg m^?3, in the embalming room. The levels found in the corridor between the teachers?? rooms and in the entrance hall were lower than in other compartments because of their large distances to the sources of FA and better ventilation. The other rooms presented higher levels of FA because of the activities carried there (embalming and dissection procedures). Even in the rooms that showed the lowest levels of FA, the values found were higher than those established by all international guideline limits, except the Brazilian legislation limit, although, the concentration level in the embalming room was even greater than the Brazilian guideline. These concentrations are 100?C1,000-fold higher than those reported in an FA outdoor study. The exposure levels of monitors and students ranged from 1.89 to 4.82 mg m^?3, indicating that current practices at the Morphology Department at the university would represent a health risk. The simultaneous monitoring of area concentrations and personal exposure showed that the characteristics of classes and of cadavers?? parts, the number of students in the room and even the activities of the monitors influence the FA concentrations.

Conclusion

This study revealed that the concentration of FA was low in the ventilated areas of the Morphology Department, and that the personal exposure when the person was close to the cadavers during the dissection procedure was higher than the mean FA concentration. This should be considered in the risk assessment of FA during these activities without effective protection equipment. It is suggested that the Brazilian legislation of exposure to formaldehyde requires an urgent update considering international legislation.