Changes of AhR-mediated activity of humic substances after irradiation

Humic substances (HS) and natural organic matter (NOM) are natural organic compounds ubiquitous in the environment. However, some studies indicate that both HS and NOM can act as xenobiotics, e.g. induce hormone-like effects in fish, amphibians and invertebrates. Molecules of these substances contain a number of aromatic rings and conjugated double bonds--the so called chromophores. Irradiation of dissolved HS and NOM can lead to a series of photochemical reactions which can act on these substances itself, or on other substances present in aquatic environment along with HS and NOM such as e.g. xenobiotics. In our previous study, we have found significant interactions of five humic acids (HA) with cytosolic aryl hydrocarbon receptor (AhR) in an in vitro bioassay based on H4IIE-luc cells. In the present study, we have studied the changes in AhR-mediated activities both of HS and NOM after irradiation that simulated natural solar light. Nine different HS and two NOM samples were irradiated in Pyrex tubes with a medium-pressure mercury lamp for a duration of 0 to 52 h (which corresponds to 0-52 d natural solar radiation). Original concentrations of the samples were 50 mg L(-1), and the greatest concentration of HS and NOM photoproducts subsequently tested in the bioassay was 17 mg L(-1), which is an environmentally relevant concentration. After irradiation the absorbances of all the samples were less than the original materials. The AhR-mediated activity of the HA-Fluka and HA Sodium Salt were partially decreased by irradiation. The activities of other HS and NOM, that were either AhR-active or -inactive were not changed by irradiation. The results of the study demonstrate that AhR-mediated activities of two active HA is caused by both photo-stable and photo-labile AhR activators, while the other three active HA contain only photo-stable AhR activators. Potential mechanisms of the observed irradiation-induced changes in AhR-mediated activities are discussed.     

Perfluorinated chemicals in blood of residents in Catalonia (Spain) in relation to age and gender: a pilot study

Fluorinated organic compounds (FOCs) are a group of chemicals widely used as surfactants, lubricants, polymers, and fire-fighting foams. Recent studies have shown the ubiquitous distribution of FOCs in the environment, wildlife, and humans. We here report the results of a pilot study conducted to provide preliminary data on the levels of 13 FOCs in the blood of 48 residents in Catalonia, Spain, in relation to gender and age (25+/-5 and 55+/-5 years). The highest mean concentration was obtained for perfluorooctane sulfonate (PFOS, 7.64 ng/ml), followed by perfluorohexane sulfonate (PFHxS, 3.56 ng/ml) and perfluorooctanoic acid (PFOA, 1.80 ng/ml). Four other FOCs showed mean levels between 0.30 and 0.44 ng/ml, whereas those of the remaining 6 compounds were below the detection limit. Regarding gender, the blood levels of PFHxS and PFOA were significantly higher (p<0.05) in men than in women, while differences according to age were only noted for PFHxS (p<0.05) and perfluorooctane sulfonamide (PFOSA) (p<0.001), for which the levels were higher in the younger (25+/-5 years) group of subjects. A significant correlation between PFOS levels and those of the remaining detected FOCs (except PFDA) was found. In general terms, the current FOC concentrations were lower than those found in recent studies concerning levels of these chemicals in human blood and serum of subjects from different countries.     

137Cs in the Danish Wadden Sea: contrast between tidal flats and salt marshes

The 137Cs activity of salt marsh and tidal flat sediments of the northern part of the European Wadden Sea was studied based on a comprehensive dataset of 210Pb dated cores. The 137Cs inventory of salt marsh sediments shows a major peak corresponding to the Chernobyl accident in 1986, and a minor peak located in the late 1960s interpreted as the combined effect of atmospheric testing of nuclear weapons. Emissions from the nuclear reprocessing plant Sellafield are not reflected as peaks in 137Cs activity, but may contribute to the rising 137Cs activity in the years prior to 1986. The 137Cs activity of tidal flat sediments differs from salt marsh sediment in two respects. First, the activity is much lower and, second, the major peak in the 1980s is located in the beginning instead of in the middle of the decade. The differences in 137Cs inventory between the two environments are interpreted to result from repeated cycles of deposition/resuspension and mixing on tidal flats. A simple model illustrating the consequence of mixings returns an apparent shift of major peaks in 137Cs activities backwards in time corresponding to the mixing depth divided by the deposition rate.     

The transfer of 239/240Pu to cow milk

In summer 1993 we measured the transfer of (239/240)Pu to milk from herbage from a pasture located 5 km from the Chernobyl nuclear power plant. In one treatment cows were allowed to graze freely on the pasture. In a second treatment, cows were fed herbage collected from the pasture in stalls. The milk transfer coefficient; F(m) did not vary significantly between treatments and the mean value of 7.5x10(-6)d l(-1) was higher than previously reported values. Despite many values of F(m) for Pu in the literature we identified few relevant original data sets. Transfer coefficient values for Pu are only appropriate when used in conjunction with a specified time period or an appropriate model which allows for the biological half-life. We recommend for screening purposes an F(m) value of 1x10(-5)d l(-1) for Pu, with an order of magnitude lower value being appropriate for cows which are only exposed for one grazing season.     

The value of Seasonal Correction Factors in assessing the health risk from domestic radon: a case study in Northamptonshire, UK

Following an intensive survey of domestic radon levels in the United Kingdom (UK), the former National Radiological Protection Board (NRPB), now the Radiation Protection Division of the Health Protection Agency (HPA-RPD), established a measurement protocol and promulgated Seasonal Correction Factors applicable to the country as a whole. Radon levels in the domestic built environment are assumed to vary systematically and repeatably during the year, being generally higher in winter. The Seasonal Correction Factors therefore comprise a series of numerical multipliers, which convert a 1-month or 3-month radon concentration measurement, commencing in any month of the year, to an effective annual mean radon concentration. In a recent project undertaken to assess the utility of short-term exposures in quantifying domestic radon levels, a comparative assessment of a number of integrating detector types was undertaken, with radon levels in 34 houses on common geology monitored over a 12-month period using dose-integrating track-etch detectors exposed in pairs (one upstairs, one downstairs) at 1-month and 3-month resolution. Seasonal variability of radon concentrations departed significantly from that expected on the basis of the HPA-RPD Seasonal Correction Factor set, with year-end discontinuities at both 1-month and 3-month measurement resolutions. Following this study, monitoring with electrets was continued in four properties, with weekly radon concentration data now available for a total duration in excess of three and a half years. Analysis of this data has permitted the derivation of reliable local Seasonal Correction Factors. Overall, these are significantly lower than those recommended by HPA-RPD, but are comparable with other results from the UK and from abroad, particularly those that recognise geological diversity and are consequently prepared on a regional rather than a national basis. This finding calls into question the validity of using nationally aggregated Seasonal Correction Factors, especially for shorter exposures, and the universal applicability of these corrections is discussed in detail.     

An in vitro/in vivo screening assay as a sensitive tool to assess endocrine disruptive activity in surface water

Adult male fathead minnow were exposed for 14 or 28-days under flow-through conditions to undiluted filtered water samples from the rivers Meuse and Rhine in the Netherlands. The experiment included two vessels per treatment each containing 10 fish and samples of five fish were taken after 14 and 28 days. Additional groups were exposed to 17alpha-ethinylestradiol (EE2) as a reference and untreated drinking water as a negative control. Major endpoints examined included induction of vitellogenin (VTG) synthesis, VTG mRNA activity, hepato- and gonadosomatic indices (HSI and GSI) and gonadal histology. No significant difference was recorded in body weight or mean GSI values between the various treatments. Only exposure to Meuse water resulted in significantly higher HSI means after 14 days. Histological examination showed no apparent effects on gonadal tissue except for eosinophilic blood plasma in fish exposed to Meuse water or EE2. After 14 and 28 days, elevated VTG and VTG mRNA levels were measured in most livers of the fish exposed to Meuse water, but not in the fish exposed to Rhine water. This was confirmed by measuring estrogenic responses in the in vitro ER CALUX assay. Induction of VTG synthesis proved to be the most sensitive endpoint in the Non Spawning Male Fish Assay for in vivo detection of bio-available estrogenic activity supplementary to a sensitive in vitro assay. The other endpoints examined varied too much and required a higher number of fish or replicates to achieve sufficient power for statistical testing making them less animal friendly.     

Presence, biotransformation and effects of sulfophenylcarboxylic acids in the benthic fish Solea senegalensis

The presence of linear alkylbenzene sulfonates (LAS) and their degradation intermediates, sulfophenylcarboxylic acids (SPCs), with concentrations up to 100 ppb has been found in surface waters taken from the estuary of the river Guadalete (Cádiz, SW of Spain). Higher concentrations were found at the sampling site located adjacent to the discharge outlet of a wastewater treatment plant (WWTP). The concentrations decreased downstream to a few ppb as a result of dilution, sorption, and degradation processes, which were taking place along the estuary. Once the presence of both xenobiotics was confirmed in the environment, an in vivo assay was conducted to study their biotransformation and effects in the benthic fish Solea senegalensis. A flow-through system was employed, consisting of an exposure phase (120 h) with environmental levels of the surfactant (200, 500 and 800 microg/L of 2?C(10)LAS), followed by a depuration stage (72 h). The generation of SPCs has been quantified during these phases in both water and fish, with LAS biotransformation shown in all cases. The antioxidant enzymes catalase (CAT), glutathione peroxidase (GPX), glutathione reductase (GR), the phase II enzyme glutathione S-transferase (GST), and the phase III acid and alkaline phosphatases (AcP, ALP) were also estimated and utilized as biomarkers.     

Distribution of organotin compounds in the bivalves of the Aegean Sea, Greece

Five bivalve species--Mytilus galloprovinciallis (Mediterranean mussels), Venus gallina (stripped venus), Modiola barbatus L. (bearded horse mussels), Pecten jacobeus (scallops) and Callista chione (hard clams)--were collected from seven areas in Aegean Sea, Greece, between August 2001 and January 2003 and analyzed for organotins (OTs). The concentrations (as geometric means) found were 17.1 ng g-1 for tributyltin (TBT), 18.8 ng g-1 for dibutytltin (DBT), 7.8 ng g-1 for monobutyltin (MBT) and 13.0 ng g-1 for triphenyltin (TPhT) (wet weight), which are at similar or lower levels than those reported worldwide. Studying OTs distribution between different bivalve species, lower concentrations were observed in mediterranean mussels, possibly due to their growth in water column (grown on sea net pens in mussel farms), in contrast to the free-ranging species, collected from fishing grounds. Concentrations of the OTs in the examined bivalves varied seasonally.     

Evaluation of accuracy of linear regression models in predicting urban stormwater discharge characteristics

Stormwater runoff has been identified as a source of pollution for the environment, especially for receiving waters. In order to quantify and manage the impacts of stormwater runoff on the environment, predictive models and mathematical models have been developed. Predictive tools such as regression models have been widely used to predict stormwater discharge characteristics. Storm event characteristics, such as antecedent dry days （ADD）, have been related to response variables, such as pollutant loads and concentrations. However it has been a controversial issue among many studies to consider ADD as an important variable in predicting stormwater discharge characteristics. In this study, we examined the accuracy of general linear regression models in predicting discharge characteristics of roadway runoff. A total of 17 storm events were monitored in two highway segments, located in Gwangju, Korea. Data from the monitoring were used to calibrate United States Environmental Protection Agency＇s Storm Water Management Model （SWMM）. The calibrated SWMM was simulated for 55 storm events, and the results of total suspended solid （TSS） discharge loads and event mean concentrations （EMC） were extracted. From these data, linear regression models were developed. R2 and p-values of the regression of ADD for both TSS loads and EMCs were investigated. Results showed that pollutant loads were better predicted than pollutant EMC in the multiple regression models. Regression may not provide the true effect of site-specific characteristics, due to uncertainty in the data.     

Origin of major ions in monthly rainfall events at the Bamenda Highlands, North West Cameroon

Rainwater characteristics can reveal emissions from various anthropogenic and natural sources into the atmosphere. The physico-chemical characteristics of 44 monthly rainfall events （collected between January and December 2012） from 4 weather stations （Bamenda, Ndop plain, Ndawara and Kumbo） in the Bamenda Highlands （BH） were investigated. The purpose was to determine the sources of chemical species, their seasonal inputs and suitability of the rainwater for drinking. The mean pH of 5 indicated the slightly acidic nature of the rainwater. Average total dissolved solids （TDS） were low （6.7 mg/L）, characteristic of unpolluted atmospheric moisture/air. Major ion concentrations （mg/L） were low and in the order K＋ 〉 Ca2＋ 〉 Mg2~ 〉 Na＋ for cations and NO3 〉〉 HCO3 〉 SO] 〉 CI- 〉 PO3- 〉 F- for anions. The average rainwater in the area was mixed Ca-Mg-SO4-CI water type. The CI-/Na＋ ratio （1.04） was comparable to that of seawater （1.16）, an indication that N a＋ and CI originated mainly from marine （Atlantic Ocean） aerosols. High enrichments of Ca2＋, Mg2＋ and SO2- to Na＋ ratios relative to seawater ratios （constituting 44% of the total ions） demonstrated their terrigenous origin, mainly from Saharan and Sahelian arid dusts. The K＋/Na＋ ratio （2.24）, which was similar to tropical vegetation ash （2.38）, and NO3 was essentially from biomass burning. Light （〈 100 mm） pre-monsoon and post-monsoon convective rains were enriched in major ions than the heavy （〉 100 mm） monsoon rains, indicating a high contribution of major ions during the low convective showers. Despite the acidic nature, the TDS and major ion concentrations classified the rainwater as potable based on the WHO guidelines.