Assessment of the risk of solar ultraviolet radiation to amphibians. III. Prediction of impacts in selected northern midwestern wetlands

Solar ultraviolet radiation, especially UVB (280-320 nm), has been hypothesized to be at least partially responsible for adverse effects (e.g., declines and malformations) in amphibian species throughout the world. Evaluation of this hypothesis has been limited by the paucity of high-quality UV dose-response data and reliable estimates of typical UV doses that occur in amphibian habitats. In this preliminary risk assessment for effects of UV radiation on amphibians, dose-response relationships quantified in outdoor experiments were compared with UV exposure estimates for 26 wetlands in northern Minnesota and Wisconsin. A comparison of wetland doses, derived from model prediction, historical data, and dissolved organic carbon (DOC) characterization, with experimental effects levels for green (R. clamitans), northern leopard (R. pipiens), and mink (R. septentrionalis) frogs indicated that the risk of mortality and malformations due to UV exposure is low for the majority of wetlands evaluated. Wetland UV dose, averaged over the entire breeding season, exceeded effects doses for mortality for all three species in two of the 26 wetlands examined and for one species in an additional wetland. On the basis of evidence that shorter term doses caused mortality in amphibian larvae, 3-day doses were also evaluated. In three of the wetlands examined, 3-day doses in excess of 85% of full sunlight (the level that appeared to trigger effects in controlled experimentation) occurred at frequencies ranging 22-100% for all three species and at frequencies ranging from 15% to 58% for R. pipiens and R. septentrionalis in three additional wetlands. Risk of malformation in R. pipiens was apparent in five of the 26 wetlands evaluated. Overall, estimated UVB doses in 21 of the wetlands never exceeded experimental effects doses for mortality or malformations. These results suggest that most amphibians are not currently at significant risk for UVB effects in northern Minnesota and Wisconsin wetlands. However, continued reduction of ozone and other global climate change effects may increase UV doses in wetlands, suggesting that the risk of UV to amphibians should continue to be monitored and studied.     

Simulated sunlight action spectra for inactivation of MS2 and PRD1 bacteriophages in clear water

Action spectra for simulated sunlight were measured in clear water for two viruses: PRD1, a double-stranded DNA bacteriophage, and MS2, a single-stranded RNA bacteriophage. Viruses were diluted into phosphate buffered saline (20 mM PBS, pH 7.5) and exposed for 22 h to simulated sunlight either directly or through one of six glass filters with 50% cutoff wavelengths ranging from 280 to 350 nm. Virus survival was measured using the double agar layer plaque method. Both UVA (320-400 nm) and UVB (280-320 nm) light were found to contribute to PRD1 inactivation, while only UVB inactivated MS2. A computational model was developed for interpreting these action spectra with 3-nm resolution. Using these methods, we provide detailed estimates of the sensitivity of MS2 and PRD1 to photoinactivation from 285 to 345 nm. The resulting sensitivity coefficients can be combined with solar spectra to estimate inactivation rates in clear water under different sunlight conditions. This approach will be useful for modeling the inactivation of viruses and other microorganisms in sunlit natural and engineered systems.     

Assessment of the risk of solar ultraviolet radiation to amphibians. II. In situ characterzation of exposure in amphibian habitats

Ultraviolet B (UVB) radiation has been hypothesized as a potential cause of amphibian population declines and increased incidence of malformations. Realistic studies documenting UV irradiance or dose have rarely been conducted in wetlands used by amphibians. Our data indicates that 99% of UVB is attenuated in the top 5-20 cm of wetlands in our study region (northern Minnesota and Wisconsin). Furthermore, vegetation and other habitat features have substantial impacts on local UVB irradiance levels and dose. UVB attenuation in the water columns of our wetlands is controlled by the specific absorption of dissolved organic carbon (DOC), and consequently, UVB attenuation is best predicted by simple laboratory absorbance measurements such as bulk water color (absorbance at 440 nm) or wavelength-specific absorbance coefficients. Seasonal data indicate thatthe UVB absorption by early and mid-season DOC is higher than that of late summer and fall DOC, suggesting increased protection from UVB during the potentially sensitive stages of amphibian development. In addition to dissolved components, our model indicates that suspended solids play a small role in UVB attenuation in our wetlands but apparently only at high concentrations. Models predicting UV attenuation in wetlands should be used cautiously and should consider temporal variability, given the volatility and dynamic nature of water column characteristics in wetlands. Organism behavior is a critical but poorly understood phenomenon that must be addressed for development of an accurate UV exposure risk model for amphibians.     

Relationship between UVA protection and skin response to UV light: proposal for labelling UVA protection

Definition and validation of a most relevant method to assess ultravoilet A (UVA) protection is a major concern for industry, authorities and consumers. However, due to the lack of knowledge about all the biological phenomena involved, the level of UVA protection needed, the ways to assess and label it, remain controversial. In order to overcome this situation, the paper deals with the outcomes of a mathematical model to calculate the distribution between ultravoilet B (UVB) and UVA components of skin responses to UV light. Mathematical calculations of UVB and UVA erythemal components of skin response to sunlight are developed from the well-known determination procedure to calculate the sunburn protection factor (SPF) of sunscreens. The model establishes the relationship between the UVA component of skin erythemal response to overall UV radiation received from sunlight and the ratio SPF/PFAe (erythemal protection factor) where SPF is the product and PFAe is related to the UVA part of the sunlight. Depending on the efficacy profile of sunscreens, the skin erythemal response may be mainly promoted by UVB rays as it normally occurs in unprotected skin or on contrary by UVA rays. Therefore, the efficacy profile of sunscreens defines the deepness where biological events induced by sunlight take place. This new relationship pinpoints the tremendous importance of the protection afforded by sunscreen products in the UVA range when erythema is taken as biological response. By extrapolation of the model to any other biological skin response it becomes possible to predict how to improve the efficiency of sunscreen products in the future. UVA protection afforded by sunscreens should be improved until reaching the same level as the SPF protection factor so that all UV-induced biological responses could be prevented or lowered at the same extend. To enforce this improvement, a proposal to classify sunscreen products in relation with their UVA protection is made.     

Reconstructed human epidermis as an efficient tool in the evaluation of the effects of UV irradiation and of the photoprotective capacities of a sunblock

In this study, we used a spectroscopic method, found effective in measuring sunscreen photo-degradation results in terms of a photoabsorption decrease. The traditional approach was to measure variations in well-known parameters such as the absolute in vitro sun protection factor (SPF) or the relative UVA/UVB ratio after a controlled dose of UV radiation. However, these parameters fail to fully reflect the product's photochemical behavior. Variation in the SPF mainly depicts changes in UVB filtration, and variation in the relative parameter UVA/UVB ratio can be subjected to misinterpretation, as is the case for products in which a parallel loss of photoabsorption is observed in the UVA and UVB regions. In our laboratory, we developed a new approach using pure spectroscopic UVA and UVB attenuation factors called UVA attenuation factor and UVB attenuation factor. Attenuation factors are defined here as the inverse of the arithmetic mean of the transmittance data, taken either from the UVB region (290–320 nm, 1 nm steps) or the UVA region (320–400 nm, 1 nm steps). Using these two new spectroscopic indices, the photochemical behavior of a sunscreen formula can be assessed in each UV region. The general procedure consists of applying two UV doses to a film of sunscreen previously spread on a roughened polymethylmethacrylate plate and then measuring the UV transmission versus wavelength before and after the irradiation process. We tested different UV filters in a cosmetic base to demonstrate the efficacy of the method.     

Comparative evaluation of different substrates for the in vitro determination of sunscreen photostability: spectrophotometric and HPLC analyses

Polymethylmethacrylate (PMMA) plates and Transpore^TM tapes were compared as substrates for the in vitro evaluation of photostability of commercial sunscreen products. The sun care preparations were applied respectively on Transpore^TM tapes and PMMA plates and their sun protection factors (SPF) and UVA protection parameters [UVA/UVB ratio, critical wavelength, UVA protection factor (UVA‐PF)] were measured by transmission spectroscopy, before and after irradiation with simulated sunlight. No significant differences were observed in the UV protection parameters measured on Transpore^TM tapes or PMMA plates, before exposure to the solar simulator. Conversely, after irradiation, the SPF values of the sun care products exhibited marked variations between the two substrates, the decrease in SPF being greater on PMMA plates (31.3–63.1%) than on Transpore^TM tapes (10.4–23.8%). Differences between the two substrates were detected also for the UVA protection parameters, although they were significant only for the UVA‐PF. The tested samples were assayed also by high‐performance liquid chromatography (HPLC) to assess the extent of photodegradation of the UV filters present in the examined formulations. The results showed that for the PMMA plates, the light‐induced decrease in SPF, as determined by spectrophotometry, fitted well with the percentage loss of ethyl hexyl methoxycinnamate (the only photounstable UVB filter present) measured by HPLC. Moreover, for the PMMA substrate, the UVA‐PF percentage reduction was consistent with the percentage degradation of butyl methoxydibenzoylmethane (the only photounstable UVA filter present) determined by HPLC. On the other hand, poor correlation between spectrophotometric and HPLC analyses was observed on Transpore^TM tapes. Therefore, PMMA plates are more reliable than Transpore^TM tapes as substrates for in vitro photodegradation tests of sunscreen products by transmission spectroscopy.     

Update on ultraviolet A and B radiation generated by the sun and artificial lamps and their effects on skin

Solar radiation, especially ultraviolet A (UVA) and ultraviolet B (UVB), can cause damage to the human body, and exposure to the radiation may vary according to the geographical location, time of year and other factors. The effects of UVA and UVB radiation on organisms range from erythema formation, through tanning and reduced synthesis of macromolecules such as collagen and elastin, to carcinogenic DNA mutations. Some studies suggest that, in addition to the radiation emitted by the sun, artificial sources of radiation, such as commercial lamps, can also generate small amounts of UVA and UVB radiation. Depending on the source intensity and on the distance from the source, this radiation can be harmful to photosensitive individuals. In healthy subjects, the evidence on the danger of this radiation is still far from conclusive.     

New ex-vivo method for evaluating the photoprotective efficacy of sunscreens

The photoprotective efficacy of some topical sunscreens was determined ex-vivo by spectrophotometric assay using an irradiation monochromator and a diffuse reflectance sphere. Transmission scans were run from 400 to 290 nm through human epidermis samples before and after application of products and protection factors (PF) were calculated. The results are also expressed as the percentage of the radiation stopped by the products in each spectral range (UVB, short UVA and long UVA). All the formulations contained two chemical filters: butyl methoxy dibenzoyl methane and octyl methoxycinnamate in a range of concentrations. Estimates of the effectiveness of all products were higher than results in humans when calculated by this ex-vivo technique. Due to its high discriminant power, this method constitutes a useful tool in the formulation of sunscreens.     

In vivo and in vitro assessment of UVA protection by sunscreen formulations containing either butyl methoxy dibenzoyl methane, methylene bis-benzotriazolyl tetramethylbutylphenol, or microfine ZnO

The UVA-attenuating properties of the three UVA filters butyl methoxy dibenzoyl methane (BMDBM), methylene bis-benzotriazolyl tetramethylbutylphenol (MBBT), and microfine zinc oxide (ZnO), are compared. For this purpose persistent pigment darkening (PPD) as an in vivo method as well as different in vitro approaches like the UVA/UVB ratio, the critical wavelength, and the Australian standard have been used. For the case of the UVA/UVB ratio and the critical wavelength the behaviour was also assessed after irradiation with 10 minimal erythemal doses (MED). Sunscreen formulations were manufactured containing either one of these UVA filters or combinations of one UVA filter and a constant amount of UVB filter. The concentration of the respective UVA filter was varied. BMDBM was dissolved in the oil phase of the formulations. MBBT, which is produced as particulate organic UVA-filter dispersion with average particle size smaller than 200 nm, was added to the aqueous phase. The microfine ZnO was incorporated into the oil phase. If no additional UVB filters were present, UVA/UVB ratio and critical wavelength stayed almost constant, independent of UVA-filter content. With constant levels of additional UVB filters these parameters increased with UVA-filter concentration. In contrast to the behaviour of the UVA/UVB ratio, which appeared to be a sensitive measure for the UVA protection in relation to UVB protection in almost the whole ranges of UVA-filter concentrations, the critical wavelength approached saturation already at low UVA-filter levels. The UVA-protection factors (UVA-PF) obtained from the in vivo studies increased with the concentration of the UVA filter in the formulations. Formulations, which showed UVA-PFs > or = 4 in most cases met also the conditions of the Australian Standard. An irradiation dose of 2.5 kJ m(-2) (10 MED) induced significant decreases of UVA/UVB ratio or critical wavelength only with some BMDBM formulations, indicating a loss of UVA protection in those cases.     

A comparison of the effect of supplementation and sunlight exposure on serum vitamin D and parathyroid hormone: A systematic review and meta-analysis

Abstract

Background: Supplementation and getting sunlight exposure are two treatments for vitamin D deficiency. However, studies reported conteroversial findings regarding the efficacy of these two methods.

Objective: To compare the effect of oral vitamin D supplementation with sunlight exposure on serum vitamin D and parathyroid hormone (PTH).

Methods: A computer-based literature search through PubMed, Scopus and Google scholar search engines was conducted until April 2019 to find clinical trials which compared the effect of oral vitamin D supplementation with sunlight exposure on serum vitamin D and PTH. Means for serum 25-hydroxy vitamin D3 (25(OH) D3) and PTH concentration were extracted. A subgroup analysis was used to detect potential sources of inter-study heterogeneity. Mean differences (MD) were analyzed using a random-effects model (the DerSimonian-Laird approach).

Results: A total of seven papers were included in the meta-analysis. Pooled analysis showed that vitamin D supplementation significantly elevated levels of serum 25(OH) D3 in comparison with sunlight exposure (MD: 8.56nmol/l, 95%CI: 4.15, 12.97, T² = 40.32%, H² = 9.45%, P for heterogeneity p?<?0.001). Also, the difference between the effect of vitamin D supplementation and sun exposure was lower in studies which used UVB radiation compared with studies which applied direct sunlight (MD: 11.65?nmol/l, 95%CI: 7.02, 16.28; P for between subgroup heterogeneity = 0.001).

Conclusion: Vitamin D supplementation was more effective than sun exposure at increasing serum 25(OH) D3. The difference between efficacy of vitamin D supplementation and sun exposure was lower in studies which used long-term sun exposure or applied UVB treatment instead of direct sunlight.     

New data on skin photoprotection

Absorbed ultraviolet (UV) radiation is responsible for photochemical degradation of the skin. Erythema is the most apparent result of the sunburn reaction, but the most serious results are photoaging and photocarcinogenesis, largely mediated by reactive oxygen species (ROS). To prevent these light-induced reactions, effective protection against both UVB and UVA radiations are essential. The aim of this study was to evaluate the protective efficacy against both UVB and UVA rays of three sunscreen preparations (two creams and one lotion), evaluating also their water resistance. For this purpose SPF (Sun Protection Factor) and UVA protection were tested, respectively, on 40 and 20 pre-selected volunteers (male and female, < 22-years-old with skin types I, II and III) by the Colipa test method and the Mark et al. methodology. A wash-off test was also conducted to determine the resistance to water. Results obtained showed that the three formulations studied underline interesting SPF values from about 20-30 with an excellent correlation between visual and colorimetric results obtained (P < 0.05). The controlled decrease in effectiveness of only 20% after 10 min washing proved that the vehicle is also an important factor in determining the protective efficacy. From the obtained data, the studied formulations seem to have an high SPF and UVA protection efficacy together with a good water resistance. According to several other studies, it is possible to confirm therefore that the regular use of these sunscreens may certainly reduce the harmful effect caused by long-term exposure to UVB and UVA radiation.     

Fading of artificial hair colour and its prevention by photofilters

Fading of artificial hair colour has been investigated by simulating actual usage conditions through exposure to artificial radiation in a weatherometer, with 0.35 mW (m(2)nm)(-1) at 340 nm, for 16-48 h, and by periodical washing. Hair colour was produced by using commercial two-part, permanent hair dyes with light auburn, medium auburn and dark auburn shades. Formulations based on red couplers, such as 4-amino-2-hydroxytoluene and 1-naphthol, as well as primary intermediates, such as 1-hydroxyethyl-4,5-diamino pyrazole sulphate, were employed. Results indicate that the extent of fading, as measured by the total colour change parameter, dE, is greatest for coloured hair subjected to both irradiation and shampooing, and significantly smaller for hair undergoing only irradiation or washing. Colour loss has been also found to be dependent upon the hair type employed, with coloured natural white and bleached hair undergoing much greater change than coloured brown hair. It has been also shown that hair colour based on pyrazole intermediates displayed the deepest fading as a result of shampooing (dE 4-6 after 10 shampooings) and irradiation per shampooing (dE 14-16 after 32 h of light exposure and four shampooings). The contribution of UV light (UVB + UVA) to the artificial hair-colour loss was found experimentally to be dependent upon the irradiation dose and varied from 63% at 16 h of irradiation time to 27% at 48 h of light exposure. The theoretical extent of photoprotection by a formulation was assessed by calculating the percentage of UV light it attenuates in the wavelength range from 290 to 400 nm. The results indicate that UVB photofilters, such as octyl methoxy cinnamate, absorb <25% of the total UV irradiation at concentrations as high as 30 mg (g hair)(-1). UVA absorbers were found to be more effective, with benzophenone-3 and benzophenone-4 absorbing about 40% of UV at the same concentration. Corresponding experimental data were in reasonable agreement with the theoretical predictions. The data are also presented for colour protection with treatments containing two photo-absorbers: benzophenone-3-ZnO; benzophenone-4-ZnO; octyl methoxy cinnamate-ZnO; and dimethylpabaimidopropyl laurdimonium tosylate-benzophenone-3.     

Protective effect evaluation of free radical scavengers on UVB induced human cutaneous erythema by skin reflectance spectrophotometry

This paper assesses the suitability of UVB induced skin erythema measured by reflectance spectrophotometry in humans as a model for differentiating topical efficacy of free radical scavengers. Two different formulations (aqueous gels and O/W emulsions) of each active compound (tocopherol, tocopherol acetate, superoxide dismutase (SOD), glutathione, ascorbyl palmitate) were tested on healthy human volunteers before and after skin exposure to UVB radiation. Skin erythema was monitored by calculating erythema index values from the skin spectral data obtained using a reflectance spectrophotometer. The free radical scavengers tested were not able to inhibit UVB induced skin erythema from both formulations when they were topically applied before UVB irradiation. Applying the free radical scavenger formulations after skin exposure to UVB radiation, glutathione and SOD showed the best ability in inhibiting the induced erythema (percentage inhibition 53.3 and 41.6%, respectively from gels). Tocopherol and tocopherol acetate inhibited UVB skin erythema by 27% while ascorbyl palmitate showed a poor efficacy. For all the active compounds tested, no significant difference was observed comparing the results obtained from gels to those from emulsions. Liposomal gel formulations containing the free radical scavengers which showed the best activity (SOD and glutathione) were prepared and topically applied after skin exposure to UVB radiation. SOD and glutathione liposomal formulations were more effective than the corresponding conventional gels. The proposed model, if validated by further studies, could be useful for differentiating the effectiveness of free radical scavengers in inhibiting photoaging due to long-term sunlight skin exposure.     

Dietary acrylamide exposure among Finnish adults and children: the potential effect of reduction measures

A deterministic exposure assessment using the Nusser method that adjusts for within-subject variation and for nuisance effects among Finnish children and adults was carried out. The food consumption data covered 2038 adults (25-74 years old) and 1514 children of 1, 3 and 6 years of age, with the data on foods' acrylamide content obtained from published Finnish studies. We found that acrylamide exposure was highest among the 3-year-old children (median = 1.01 μg kg(-1) bw day(-1), 97.5th percentile = 1.95 μg kg(-1) bw day(-1)) and lowest among 65-74-year-old women (median = 0.31 μg kg(-1) bw day(-1), 97.5th percentile = 0.69 μg kg(-1) bw day(-1)). Among adults, the most important source of acrylamide exposure was coffee, followed by casseroles rich in starch, then rye bread. Among children, the most important sources were casseroles rich in starch and then biscuits and, finally, chips and other fried potatoes. Replacing lightly roasted coffee with dark-roasted, swapping sweet wheat buns for biscuits, and decreasing the acrylamide content of starch-based casseroles and rye bread by 50% would result in a 50% decrease in acrylamide exposure in adults. Among children, substituting boiled potatoes for chips and other friend potatoes and replacing biscuits with sweet wheat buns while lowering the acrylamide content of starch-based casseroles by 50% would lead to acrylamide exposure that is only half of the original exposure. In conclusions, dietary modifications could have a large impact in decreasing acrylamide exposure.     

Consequences for sun protection factors when solar simulator spectra deviate from the spectrum of the sun

The sun protection factor (SPF) of two products, one with an expected SPF of 4 and another with an expected SPF of 15 were determined, using two solar simulators: Multiport Solar UV Simulator (xenon, Solar Light, Philadelphia, PA, USA), and Supersun 5000 (metal halide, Mutzhas, Munich, Germany). The mean SPFs using the Multiport were: 4.8 for the low SPF product and 19.4 for the high SPF one. The results using the Supersun were lower: 2.6 for the low SPF product and 7.2 for the high SPF one. Relative emission spectra of the two sources were recorded using a fluorescence spectrophotometer in bioluminescence mode. Efficacy spectra were calculated and compared with the corresponding spectrum of natural sunlight. It was evident that the spectral power of the xenon source is too high in the UVB, leading to overestimation of SPFs, whereas the Supersun irradiator emits too much in the UVA, resulting in too low SPFs. Heat effects and photodegradation of UV filters are discussed as further possible reasons for the discrepancies between the experimentally determined SPFs. Our results confirm a recent publication about theoretical SPFs, calculated with emission spectra of a xenon source and spectra of the sun at different elevation angles, where the authors provide evidence that in natural sunlight the contribution of UVA to total UV radiation is twice as high as in a xenon source. This may contribute to an understanding of why sunscreens tested according to the FDA method (xenon sources) often yield higher SPFs than those obtained from European testing procedures.     

竹原纤维/毛交织花呢的防紫外线性能

为了更好发挥竹原纤维在精纺呢绒中的防紫外线性能,从新品开发的角度着手,通过对几种不同含量竹原纤维/毛交织花呢防紫外线性能的比较,证实竹原纤维含量越多,织物对紫外线反射能力越高,紫外线防护性能越好;竹原纤维含量为50%的织物,对紫外线的吸收,尤其是对UVC的反射能力较高,该织物的紫外线防护性能较好;各面料的透过率主要取决于其对紫外线的吸收率,竹原纤维含量为20%的面料对UVA、UVB的透过率最低,含量为50%的面料对UVC的透过率最低。研究结果为竹原纤维新材料在精毛纺中的应用提供了参考。     

Dietary acrylamide exposure among Finnish adults and children: the potential effect of reduction measures

A deterministic exposure assessment using the Nusser method that adjusts for within-subject variation and for nuisance effects among Finnish children and adults was carried out. The food consumption data covered 2038 adults (25–74 years old) and 1514 children of 1, 3 and 6 years of age, with the data on foods’ acrylamide content obtained from published Finnish studies. We found that acrylamide exposure was highest among the 3-year-old children (median?=?1.01?µg?kg^?1?bw^?day^?1, 97.5th percentile?=?1.95?µg?kg^?1?bw^?day^?1) and lowest among 65–74-year-old women (median?=?0.31?µg?kg^?1?bw^?day^?1, 97.5th percentile?=?0.69?µg?kg^?1?bw^?day^?1). Among adults, the most important source of acrylamide exposure was coffee, followed by casseroles rich in starch, then rye bread. Among children, the most important sources were casseroles rich in starch and then biscuits and, finally, chips and other fried potatoes. Replacing lightly roasted coffee with dark-roasted, swapping sweet wheat buns for biscuits, and decreasing the acrylamide content of starch-based casseroles and rye bread by 50% would result in a 50% decrease in acrylamide exposure in adults. Among children, substituting boiled potatoes for chips and other friend potatoes and replacing biscuits with sweet wheat buns while lowering the acrylamide content of starch-based casseroles by 50% would lead to acrylamide exposure that is only half of the original exposure. In conclusions, dietary modifications could have a large impact in decreasing acrylamide exposure.     

Continuous analysis of dissolved gaseous mercury and mercury volatilization in the upper St. Lawrence River: exploring temporal relationships and UV attenuation

The formation and volatilization of dissolved gaseous mercury (DGM) is an important mechanism by which freshwaters may naturally reduce their mercury burden. Continuous analysis of surface water for diurnal trends in DGM concentration (ranging from 0 to 60.4 pg L(-1); n=613), mercury volatilization (ranging from 0.2 to 1.1 ng m(-2) h(-1); n=584), and a suite of physical and chemical measurements were performed during a 68 h period in the St. Lawrence River near Cornwall (Ontario, Canada) to examine the temporal relationships governing mercury volatilization. No lag-time was observed between net radiation and OGM concentrations (highest cross-correlation of 0.817), thus supporting previous research indicating faster photoreduction kinetics in rivers as compared to lakes. A significant lag-time (55-145 min; maximum correlation = 0.625) was observed between DGM formation and mercury volatilization, which is similar to surface water Eddy diffusion times of 42-132 min previously measured in the St. Lawrence River. A depth-integrated DGM model was developed using the diffuse integrated vertical attenuation coefficients for UVA and UVB (K(dI UVA) = 1.45 m(-1) K(dI UVB)= 3.20 m(-1)) Low attenuation of solar radiation was attributed to low concentrations of dissolved organic carbon (mean = 2.58 mg L(-1) and particulate organic carbon (mean = 0.58 mg L(-1) in the St. Lawrence River. The depth-integrated DGM model developed found that the top 0.3 m of the water column accounted for only 26% of the total depth-integrated DGM. A comparison with volatilization data indicated that a large portion (76% or 10.5 ng m(-2) of the maximum depth-integrated DGM (13.8 ng m(-2))is volatilized over a 24 h period. Therefore, at least 50% of all DGM volatilized was produced at depths below 0.3 m. These results highlight the importance of solar attenuation in regulating DGM formation with depth. The results also demonstrate both the fast formation of DGM in rivers and the importance of understanding DGM dynamics with depth as opposed to surface waters.     

Beyond UV radiation: A skin under challenge

Since ancient times, human beings have been trying to protect their skin against the adverse effects of the sun. From the first mineral sunscreens used by Egyptians, to the current more sophisticated ultraviolet (UVA/UVB) organic sunscreens, progress has been made in terms of sun protection and deeper knowledge of skin physiology has been acquired in the process. The solar spectrum is composed of radiations of various wavelengths having specific, as well as overlapping effects on skin. UVB is mainly responsible for sunburn and DNA dimer formation that can lead to mutation. UVA generates oxidative reactions affecting DNA, proteins and lipids, and is also immunosuppressive. Recently, visible light and infrared radiation (IR) have been associated with oxidative damage and IR has been additionally linked to adverse heat effects on skin. Numerous other extrinsic factors, related to environment and lifestyle, also affect the appearance of skin, precipitating ageing. New molecular mechanisms linking sun and environmental factors to skin ageing have been identified: IR affects mitochondrial integrity and specific heat receptors also mediate some of its effects, tryptophan is a chromophore for UVB, and the aryl hydrocarbon receptor (AhR) is activated by light and xenobiotics to alter skin physiology. Integrating all these new elements is changing the way we think about skin extrinsic ageing. Is UVA/UVB sunscreen protection still enough for our skin?     

Gross photoreduction kinetics of mercury in temperate freshwater lakes and rivers: application to a general model of DGM dynamics

Previous published measurements of mercury photoreduction are for net-photoreduction, since photooxidation processes occur simultaneously. In this research we combine continuous dissolved-gaseous mercury (DGM) analysis with a photoreactor and a quartz sparger in order to derive mercury gross photoreduction rate constants for UVB and UVA irradiations. The DGM concentration in each filter-sterilized freshwater was measured at 5 min intervals over a period of 23 h. Photoreduction proceeded for the initial 200 min, after which, reducible mercury was depleted in the sample. Substantial losses in DOC fluorescence were observed during the incubations for UVA radiation but not for UVB; therefore, UVB photoreduction dynamics are not linked to a loss in DOC fluorescence. Pseudo first-order reaction kinetics fit the data well (r2 > 0.87). The rate constants appear divided between lakes and rivers with the mean lake UVB rate constant (kUVB = 8.91 x 10(-5) s(-1)), significantly less than the mean rate constant (kUVB = 1.81 x 10(-4) s(-1)) for the river samples. However, while there were differences for the UVB rates between lakes and rivers, the mean and median rate constants for UVA in lakes (kUVA = 7.76 x 10(-5) s(-1)) did not differ significantly from the mean rate constant forthe river sites (kUVA = 1.78 x 10(-4) s(-1)). Here, we propose a model for mercury photoredox dynamics for both temperate lake and river systems. The lake model was validated using principal axis analysis to compare observed and predicted DGM data (n=279) from a variety of lake sites in Nova Scotia and Central Quebec. Principal axis analysis found a linear fit (correlation = 0.81; slope = 2.13) between predicted and observed environmental DGM values when log-normalized. The constant bias on the predicted values was attributed to estimates of available reducible mercury and the effect of DGM volatilization on observed data.