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Incidence of non-melanocytic skin cancer treated in Australia.

In 1985, as part of a national random household omnibus survey by a market research company, 30,976 Australians (mostly of European origin) were asked whether they had ever been treated by a doctor for skin cancer. The treating doctor or hospital was then approached for confirmation of the diagnosis of all those people who claimed to have been so treated within the past 12 months. Demographic data were also collected, permitting analysis by age, sex, country of birth, current residence, and skin reaction to strong sunlight. Melanomas accounted for less than 5% of the tumours treated. The world standardised incidence of melanoma was 19/100,000 population. The standardised incidence of treated non-melanocytic skin cancer in Australia was estimated to be 823/100,000. The standardised rates for basal cell carcinoma and squamous cell carcinoma were 657 and 166/100,000 respectively, yielding a standardised rate ratio of about 4:1. Standardised rates based on medically confirmed cases only were 555, 443, and 112/100,000 for all non-melanocytic skin cancers, basal cell carcinomas, and squamous cell carcinomas respectively. Significant differences and trends in incidence were noted with respect to age and sex. Rates in men were higher than those in women but significantly so only after the age of 60. People born in Australia had a rate of 936/100,000 compared with 402/100,000 in British migrants. Rates for non-melanocytic skin cancer showed a gradient with respect to latitude within Australia. The rate in people residing north of 29 degrees S was 1242/100,000 compared with a rate of 489/100,000 in those living south of 37 degrees S. A person's skin reaction to strong sunlight was a good indicator of the risk of skin cancer, tanning ability being inversely related to its incidence. The rate in those who always burnt and never tanned when exposed to strong sunlight was 1764/100,000 compared with a rate of 616/100,000 in those who always tanned and never burnt. These findings have important implications for public education programmes in relation to exposure to sunlight in Australia.

Adolescent↗

Effects of environmental factors present in the St. Lawrence Estuary (Quebec, Canada) on experimental survival of Salmonella salamae as determined by flow cytometry.

Survival of Salmonella salamae in the St. Lawrence Estuary was studied experimentally during an oceanographic cruise using in situ exposure diffusion chambers. The abundance distribution (colony-forming units) of culturable S. salamae on media was compared with the distribution of cells enumerated by flow cytometry. Flow cytometry was also used to characterize the size distribution and DNA content of cells exposed to various environmental factors. Solar radiation, starvation, and a gradual increase in salinity led to an abrupt loss of the ability of S. salamae cells to form cultures and to a gradual reduction in the cell size and DNA content. Conversely, starvation combined with a gradual increase in salinity in the absence of sunlight led to a gradual loss of the cells' ability to form cultures and an abrupt reduction in cell size and DNA content (i.e., a rapid increase in cell damage). Mortality (i.e., a decrease in total cell count) of S. salamae placed in darkness began at a lower salinity (11.4/1000) than did the mortality of cells exposed to sunlight (23.1/1000). Therefore, the S. salamae cells exposed to sunlight seemed to be more resistant to gradual salinity stress than the cells that were not subjected to sunlight.

DNA, Bacterial↗

Clothing as solar radiation protection.

The sun is essential for life. Yet, sunlight can also be a source of such deleterious effects as sunburn, and suntanning, as well as premalignant and malignant lesions. These may all occur in individuals with normal responses to sunlight. In addition, there exist a variety of 'abnormal' photosensitivity responses to sunlight that may result from either endogenous imbalances (e.g. the porphyrias) or from added exogenous factors (e.g. drug photosensitivity). The 'normal' responses to sunlight, by and large, are produced preferentially by UVB (290-320 nm), with minor contribution by UVA (320-400 nm) wavelengths. In contrast, the 'abnormal' photosensitivity responses are, for the most part, elicited predominantly by long UVA and, in some cases, visible light. In the last 20 years or so, considerable attention has been paid to the use of fabrics as photoprotective materials. The vast majority of work in this area has been concerned with fabric protection against sunburn. In addition to in vivo measurement of fabric SPF, in vitro evaluation of fabric UPF has been carried out in numerous laboratories around the world. The UPF is estimated from the wavelength-dependent transmission of the fabric, the solar UV spectrum and the erythemal action spectrum over the wavelength region 290-400 nm. Depending on the fabric, UPF values range from 2 to several thousand. More recently, it has become clear that such environmental influences as laundering, solarization, humidity, wetting and degree of stretching may play a major role in fabric protection. Protection also may be altered by addition of dyes, UV absorbers and fluorescent whitening agents. To date, there have been relatively few studies of fabric protection for endpoints other than sunburn erythema. Yet, many fabrics that provide good protection against sunburn may provide inadequate protection against photosensitization by intrinsic or extrinsic absorbing molecules or against (pre)malignant lesions. Future work should explicity address the efficacy of protective fabrics against photosensitivity diseases that are activated by long UVA or visible wavelengths.

Dermatitis, Phototoxic↗

Molecular responses to stress induced in normal human caucasian melanocytes in culture by exposure to simulated solar UV.

Melanocytes play a central role in the response of skin to sunlight exposure. They are directly involved in UV-induced pigmentation as a defense mechanism. However, their alteration can lead to melanoma, a process where the role of sun overexposure is highly probable. The transformation process whereby UV damage may result in melanoma initiation is poorly understood, especially in terms of UV-induced genotoxicity in pigmented cells, where melanin can act either as a sunscreen or as a photosensitizer. The aim of this study was to analyze the behavior of melanocytes from fair skin under irradiation mimicking environmental sunlight in terms of spectral power distribution. To do this, normal human Caucasian melanocytes in culture were exposed to simulated solar UV (SSUV, 300-400 nm). Even at relatively high doses (until 20 min exposure, corresponding to 12 kJ/m2 UV-B and 110 kJ/m2 UV-A), cell death was limited, as shown by cell viability and low occurrence of apoptosis (caspase-3 activation). Moreover, p53 accumulation was three times lower in melanocytes than in unpigmented cells such as fibroblasts after SSUV exposure. However, an important fraction of melanocyte population was arrested in G2-M phase, and this correlated well with a high induction level of the gene GADD45, 4 h after exposure. Among the genes involved in DNA repair, gene XPC was the most inducible because its expression increased more than two-fold 15 h after a 20 min exposure, whereas expression of P48 was only slightly increased. In addition, an early induction of Heme Oxygenase 1 (HO1) gene, a typical response to oxidative stress, was also observed for the first time in melanocytes. Interestingly, this induction remained significant when melanocytes were exposed to UV-A radiation only (320-400 nm), and stimulation of melanogenesis before irradiation further increased HO1 induction. These results were obtained with normal human cells after exposure to SSUV radiation, which mimicked natural sunlight. They provide new data related to gene expression and suggest that melanin in light skin could contribute to sunlight-induced genotoxicity and maybe to melanocyte transformation.

Apoptosis↗

Latitude and incidence of ocular melanoma.

We investigated the associations between latitude and the incidence of two different types of ocular melanoma, external ocular melanoma (exposed to sunlight) and internal melanoma (not exposed to sunlight), separately. Using 1992-2002 data from the Surveillance, Epidemiology, and End Results (SEER) Program of National Cancer Institute, we identified 2142 ocular melanoma cases in non-Hispanic whites, and then regressed the incidences of various types of ocular melanomas with latitude. Our analysis indicated that the higher the latitude (away from the equator, the less sun exposure), the lower the risk of external ocular melanoma (eyelid and conjunctival melanomas) among non-Hispanic whites (P for trend = 0.018). The incidence increased 2.48 fold from 47-48 degrees to 20-22 degrees. This trend is very similar to that of skin melanoma. The incidence of internal ocular melanoma (uveal melanoma) increased significantly with increasing latitudes (the less sun exposure, P for trend < 0.0001), it increased 4.91 fold from 20-22 degrees to 47-48 degrees. The latitudinal patterns of ocular melanomas may reflect the dual effects of sunlight exposure, i.e. a mutagenic effect of direct solar radiation on external ocular melanomas and a protective effect for internal uveal melanoma, which is similar to the sun radiation protective effects for various internal malignant tumors that are not exposed to the sunlight.

Conjunctival Neoplasms↗

Survival of total coliforms in lawn irrigated with secondary wastewater and chlorinated effluent in the Mediterranean region.

Pregrown, two-month-old lawn was layered in 12 large square pots with an area of 0.25 m2 each, filled with a mixture of topsoil, peat, and sand. In late July, in the heart of the Mediterranean summer, the pots were divided into two groups, with six pots per group. On four different occasions, the pots in each group were sprinkled (surface irrigation) with 2 L of either secondary-treated wastewater (STW, group A) or chlorinated effluent (CHE, group B). Wastewater application always took place at 0700 hours. Samples of the surface soil and grass from each pot were collected at the following times: before irrigation, immediately after irrigation, two hours later (0900 hours), and four hours later (1100 hours). In the samples collected, the number of total coliforms per gram was measured using standard microbiological analyses. Temperature and sunlight intensity were also monitored. There was an increase in the coliforms population in soil and grass samples of both groups immediately after the wastewater application. In group A, the mean number of coliforms recorded in the soil samples reached mean values higher than 5000 cfu/g compared to 312 cfu/g recorded before application. The increase in group B was smaller but still significant. Two hours later, the number of coliforms was reduced substantially in all samples (e.g., group A, soil samples 477 cfu/g). Coliform inactivation is thought to result from the effect of temperature and mainly sunlight. However, four hours after application (1100 hours), there was a noticeable increase in the coliform number again, in all sample categories of both groups. Coliform reactivation could be a result of shadowing effect resulting from the thick foliage of the grass, where the microorganisms were protected by the sunlight radiation and regrowth in a friendly environment (especially of the soil) where moisture and nutrients were present. This, in addition to the fact that coliforms seemed to retain a sizable population between applications, results in three conclusions: (1) coliforms can survive in grass and soil for a substantial period of time, recovering from the destructive effect of chlorination, (2) use of STW, even during the Mediterranean summer, could result in a substantial "contamination" of lawns, without any proof that sun and temperature can reduce the coliform number, and (3) intense sunlight (up to 68 000 lux) was far more effective in coliform suppression than elevated temperature (up to 38 degrees C).

Agriculture↗

[Exposure to sun radiation as a risk factor for the occurrence of basal cell carcinoma in the Montenegrian population].

BACKGROUND/AIM: [corrected] Basal cell carcinoma (BCC) is the most frequent form of carcinomas in the whites. Among the environmental factors, the most important risk factor for its occurrence is the expasure to sun radiation. The aim of this study was to assess the role of the sun radiation in the development of basal cell carcinoma BCC in the Montenegrian population. METHODS: A case-control study was conducted in a period from 2002-2003. The study group included 100 histopatologically confirmed cases with BCC, while the control group included 100 patients from the same population, who did not present skin cancer and who were individually matched with the cases from the study group by sex and age (+/- 5 years). All the participants were interviewed using an epidemiological questionnaire. For statistical analysis, the chi-squared test and univariate logistic regression analysis were used. RESULTS: The risk for development of BCC was increased in the persons: that always had burns with no tan during the exposure to sunlight (OR = 1.75; 95% CI = 1.20-2.55; p = 0.003); that developed sunburns after two hours of the exposure to sunlight (OR = 3.72; 95% CI = 2.39-5.79; p < 0.001) that kept light tan or remained without changes in childhood and adolescence after the repeated exposures to sunlight (OR = 2.92; 95% CI = 1.89-4.52; p < 0.001) that often had severe and painful sunburns (OR = 4.48; 95% CI = 2.74-7.33; p < 0.001). CONCLUSION: Our study confirmed the significance of sunlight exposure for the development of BCC.

Aged↗

[The sun and malignant melanoma].

The aetiological role of sunlight in the development of cutaneous malignat melanoma (CMM) is still controversial. The aim of the present review is to discuss the contradictory findings and to reinterpret them in the light of recent epidemiological results. The following clinical and epidemiological features have raised doubts on an aetiological impact of sunlight in CMM development: the anatomical distribution of CMM does not closely match the body areas most exposed to sunlight, and CMM is most common during the middle decades of life (except for the subtype of lentigo maligna melanoma, which accounts for 10% of all CMM). Furthermore, no elevated CMM risk after sunburns or increased sun exposure has been detected in most of the case control studies performed so far. The most important risk factors, however, were the total number of melanocytic naevi in whole-body counts followed by such pigmentation characteristics as skin type and hair colour. On the other hand, the CMM incidence increases in white populations with increasing proximity of domicile to the equator and thus with increasing intensity of UV irradiation, and 5-10 times higher incidence rates have been reported from Australia and the southern states of the USA than from Europe. In industrialized nations with white populations a steep increase in CMM incidence has been described, with the main rise in body regions more frequently exposed to the sun in the last decades (trunk in men and boys and lower extremities in girls and women). Two results from recent epidemiological studies may help to clarify the contradictory findings above: first, sunburn in childhood and adolescence was shown in several case control studies to significantly elevate the risk of melanoma development, but further sunburn during adulthood did not contribute to any further risk elevation. Secondly, a study in Canadian school children revealed significantly higher naevus counts in subjects with numerous or severe episodes of sunburn in the previous 5 years. In conclusion, exposure to the sun in childhood and adolescence induces melanocytic naevi, which are known as markers of an elevated melanoma risk as well as possible precursors of CMM. Strategies to reduce melanoma incidence should therefore begin by restricting exposure to sunlight in young children and adolescents.

Cross-Cultural Comparison↗

Location and severity of cortical opacities in different regions of the lens in age-related cataract.

PURPOSE: To examine the distribution of cortical opacities across the lens in the Italian-American Natural History Study of Age-Related Cataract and to study the association between an index of sunlight exposure and the location of cortical cataract within the lens. METHODS: Lens photographs of one eye of 731 persons with cortical opacities (503 with pure and 228 with mixed types of opacity) were included in the analysis. A radial grid superimposed on the photographs was used to assess presence, location, and severity of wedge-shaped cortical opacities. RESULTS: Both the prevalence and the extent of cortical opacities were highest in the inferior-nasal quadrant and lowest in the superior-nasal quadrant of the lens. In polychotomous logistic regression, persons with the greatest excess areal involvement in the inferior half of the lens were more likely to have high exposure to sunlight, as measured by a sunlight index, than persons with excess involvement in the superior half of the lens (odds ratio, 1.73; 95% confidence interval 1.03, 2.93). Excess areal involvement of the inferior lens also was associated with the pure type of cortical cataract and with the total extent of the opacity. CONCLUSIONS: Age-related cortical opacities occur more frequently inferiorly than superiorly and, to a lesser extent, nasally than temporally. Possibly higher exposure of these lens segments to sunlight may explain this preferential location of cortical opacities.

Aged↗

Behavioral thermoregulation in a sexually and developmentally dichromatic neotropical primate, the black-and-gold howling monkey (Alouatta caraya).

Behavioral thermoregulation in primates may provide a means for the conservation of heat during periods of low ambient temperature and/or food shortage as well as a way to dissipate heat under hot conditions. This article focuses on behavioral thermoregulation in a sexually dichromatic primate, the black-and-gold howling monkey (Alouatta caraya). Two models have been proposed to explain the evolution of sexual dichromatism in this species: thermoregulation and sexual selection. Five hypotheses associated with thermoregulatory behaviors are tested. These are as follows: (1) energy-conserving postures are used mainly under low ambient temperatures; (2) sunny resting places are selected during periods of low temperature; (3) exposure of the less-insulated ventral region to sunlight decreases with increasing temperature; (4) black-colored adult males use energy-conserving postures, sunny places, and exposure of the ventral region to sunlight less frequently than do blonde-colored adult females; and (5) smaller individuals use energy-conserving postures, sunny places, and exposure of the ventral region to sunlight in significantly greater frequency than do larger individuals. Over a 12-month period, behavioral data were collected on a free-ranging habituated group of 15-17 howlers of all age-sex classes. Ambient temperature was measured each hour. The results indicate that during resting, howlers showed a consistent use of heat-conserving postures, showed a preference for sunny places, and exposed their ventral region to sunlight under low ambient temperatures. A preference for shady places, heat-dissipating postures, and exposure of the back were observed under high ambient temperatures. Despite sex differences in adult color patterns and differences in size between age classes, no significant age or sex differences in thermoregulatory behaviors were detected. Failure to confirm a thermoregulation model implies that sexual selection may be responsible for sexual dichromatism in this species.

Alouatta↗

Phytotoxicity assessment of diclofenac and its phototransformation products.

The occurrence of pharmaceuticals in the environment is an emerging issue. Several studies observed that the non-steroidal anti-inflammatory drug diclofenac is ubiquitously present in most of the surveyed surface waters, worldwide. Phototransformation of diclofenac was reported from laboratory assays as well as in natural water systems, raising the question of possible adverse effects of the phototransformation products of diclofenac to aquatic organisms. In this study the phytotoxicity of diclofenac exposed to natural sunlight was evaluated using synchronized cultures of the unicellular chlorophyte Scenedesmus vacuolatus. Diclofenac dissolved in ultra-pure water at 50 mg L(-1) was exposed to natural midsummer sunlight for a maximum of 145 h. Twice a day subsamples were taken for chromatography and parallel phytotoxicity assessment. Inhibition of algal reproduction of the initial diclofenac solution was in the mg L(-1) range indicating no specific toxicity of diclofenac towards S. vacuolatus. Fast degradation of diclofenac was observed with half lives between 3.3 and 6.4 h during the first and the third day of exposure, respectively. Phytotoxicity increased after 3.5 h of exposure of diclofenac to sunlight and showed a maximum of sixfold enhanced toxicity after 53 h of exposure to sunlight. Several phototransformation products were found during the experiment. The time courses of the relative concentration of three transformation products significantly correlated with enhanced phytotoxicity during the experiment. This indicates a high toxicity potential of phototransformation products of diclofenac at concentration levels that may come close to environmental concentrations of residual diclofenac after degradation. We conclude that toxicity assessment of phototransformation products should be included in the risk assessment of pharmaceuticals in the environment.

Chromatography, High Pressure Liquid↗

Interactions of Photobleaching and Inorganic Nutrients in Determining Bacterial Growth on Colored Dissolved Organic Carbon.

Abstract Bacteria are key organisms in the processing of dissolved organic carbon (DOC) in aquatic ecosystems. Their growth depends on both organic substrates and inorganic nutrients. The importance of allochthonous DOC, usually highly colored, as bacterial substrate can be modified by photobleaching. In this study, we examined how colored DOC (CDOC) photobleaching, and phosphorus (P) and nitrogen (N) availability, affect bacterial growth. Five experiments were conducted, manipulating nutrients (P and N) and sunlight exposure. In almost every case, nutrient additions had a significant, positive effect on bacterial abundance, production, and growth efficiency. Sunlight exposure (CDOC photobleaching) had a significant, positive effect on bacterial abundance and growth efficiency. We also found a significant, positive interaction between these two factors. Thus, bacterial use of CDOC was accelerated under sunlight exposure and enhanced P and N concentrations. In addition, the accumulation of cells in sunlight treatments was dependent on nutrient availability. More photobleached substrate was converted into bacterial cells in P- and N-enriched treatments. These results suggest nutrient availability may affect the biologically-mediated fate (new biomass vs respiration) of CDOC.

Journal Article↗

Photodegradation of new amino acid derivatives suitable for chelating agents in pulp bleaching applications.

The purpose of this study was to evaluate photodegradabilities of the following new low-nitrogen chelating agents: N-bis[(carboxymethoxy)ethyl]glycine (compound 1), N-bis[(1,2-dicarboxyethoxy)ethyl]glycine (compound 2) and N-bis[(1,2-dicarboxyethoxy)ethyl]aspartic acid (compound 3). At first photodegradation of these chelating agents as uncomplexed Na-compound 1-3 and Cu(II) complexes were tested, both in lake and distilled water, by exposing them to near-UV region radiation at the range of 315-400 nm. Uncomplexed Na-compounds 2 and 3 were selected to sunlight exposure experiments carried out in lake and distilled water. Compound 3 was also tested in sunlight as Cu and Ca complexes in both solutions. Photodegradation of Na(6)-compound 3 in distilled water was studied by exposing it to radiation at the wavelength of 253.7 nm. Photodegradation products were analysed by means of GC-MS (gas chromatography with mass selective detector). The results demonstrated that compound 1 was quite photostable even as Cu complex while compounds 2 and 3 were found to be photodegradable. Over 90% reduction of compound 3 was achieved during one week and 80% reduction of compound 2 in two weeks' time when they were added as Na salt to lake water and exposed to sunlight. Compound 3 as Cu complex degraded totally in the sunlight in less than one week. In the case of compound 3, the degradation rate decreased depending on the counter cation in the order Cu > Na > or = Ca. The study demonstrated that photodegradation of Na(6)-compound 3 does not result in total mineralization of the compound. A photodegradation pathway for Na(6)-compound 3 is proposed.

Amino Acids↗

Changes in ultraviolet absorbance and hence in protective efficacy against lipid peroxidation of organic sunscreens after UVA irradiation.

Owing to the spectral distribution of solar UV, the UVA component of sunlight is now believed to be the main cause of photoaging and photocarcinogenesis and is much more effective than UVB in inducing peroxidative damage. Consequently, most skin care cosmetic products now include UVA filters in their formulations along with UVB filters. These modern sunscreens should provide and maintain their initial absorbance, hence protection, throughout the entire period of exposure to sunlight. However, not all UVA and UVB filters are sufficiently photostable. In this study, we examine the correlation between the photochemical degradation of sunscreen agents under UVA irradiation, with particular reference to the UVA-absorber 4-tert-butyl-4'-methoxydibenzoylmethane, alone and in combination with other organic UV filters (2-ethylhexyl 4 methoxycinnamate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate) and their ability to prevent UVA-induced lipid peroxidation. Since antioxidants are also added to formulations to deactivate free radicals generated during UVA exposure, vitamin E and the synthetic antioxidant, bis(2,2,6,6-tetramethyl-1-oxyl-piperidine-4-yl)sebacate, a nitroxide derivative, were also included in this study. By using simple in vitro tests, the results show that a decrease in spectral absorbance of the UV filters correlates in most cases with increased UVA-induced lipid peroxidation; this depends on the specific UV absorber analysed and also on whether they are alone or in combination. Furthermore, the combined presence or absence of antioxidants has a profound effect on this oxidative event. In particular, the nitroxide appears to be a more efficient photo-antioxidant than vitamin E. Similar experiments were also performed under natural sunlight and the results obtained did not differ substantially from those performed under UVA. The results presented and discussed in this work may help in understanding the effects of UVA/UVB absorbers and antioxidants upon the level of UV-induced ROS generated under UVA exposure and in natural sunlight which could be relevant for improving the photoprotection and efficacy of skin care cosmetic formulations.

Lipid Peroxidation↗

Mutations induced by ultraviolet light.

The different ultraviolet (UV) wavelength components, UVA (320-400 nm), UVB (280-320 nm), and UVC (200-280 nm), have distinct mutagenic properties. A hallmark of UVC and UVB mutagenesis is the high frequency of transition mutations at dipyrimidine sequences containing cytosine. In human skin cancers, about 35% of all mutations in the p53 gene are transitions at dipyrimidines within the sequence 5'-TCG and 5'-CCG, and these are localized at several mutational hotspots. Since 5'-CG sequences are methylated along the p53 coding sequence in human cells, these mutations may be derived from sunlight-induced pyrimidine dimers forming at sequences that contain 5-methylcytosine. Cyclobutane pyrimidine dimers (CPDs) form preferentially at dipyrimidines containing 5-methylcytosine when cells are irradiated with UVB or sunlight. In order to define the contribution of 5-methylcytosine to sunlight-induced mutations, the lacI and cII transgenes in mouse fibroblasts were used as mutational targets. After 254 nm UVC irradiation, only 6-9% of the base substitutions were at dipyrimidines containing 5-methylcytosine. However, 24-32% of the solar light-induced mutations were at dipyrimidines that contain 5-methylcytosine and most of these mutations were transitions. Thus, CPDs forming preferentially at dipyrimidines with 5-methylcytosine are responsible for a considerable fraction of the mutations induced by sunlight in mammalian cells. Using mouse cell lines harboring photoproduct-specific photolyases and mutational reporter genes, we showed that CPDs (rather than 6-4 photoproducts or other lesions) are responsible for the great majority of UVB-induced mutations. An important component of UVB mutagenesis is the deamination of cytosine and 5-methylcytosine within CPDs. The mutational specificity of long-wave UVA (340-400 nm) is distinct from that of the shorter wavelength UV and is characterized mainly by G to T transversions presumably arising through mechanisms involving oxidized DNA bases. We also discuss the role of DNA damage-tolerant DNA polymerases in UV lesion bypass and mutagenesis.

5-Methylcytosine↗

Photodegradation of polychlorinated dibenzo-p-dioxins and dibenzofurans in aqueous solutions and in organic solvents.

Aqueous solutions of selected polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were prepared using a generator column and exposed to UV (300 nm) light in the laboratory and to sunlight in an outdoor environment. In the laboratory, additional exposures were also carried out using 60% acetonitrile/water solutions. At 300 nm di- and tetra PCDDs had higher first-order photodegradation rate constants in 60% acetonitrile/water than in pure water. The solvent effect was reversed for PCDFs. These results may be a reflection of the higher polarity of PCDFs compared to PCDDs. In both the indoor and outdoor exposures photodegradation rates decreased with increasing concentrations of chlorination. However, OCDF exposed to 300 nm light in 60% acetonitrile/water and to sunlight in pure water photodegraded more rapidly than tetra CDF. Photolysis rates in sunlight were considerably slower (t(1/2) of 6.4-23 h) than photolysis rates at 300 nm in the laboratory (t(1/2) of 4.3-680 min), reflecting the lower intensity of sunlight in the 300 nm region of the UV/Vis spectrum. The extent of dechlorination of the PCDDs/PCDFs was less than 20% and reductive dechlorination does not appear to be a major process in the photodegradation of PCDDs/PCDFs in aqueous solutions.

Benzofurans↗

Abiotic production of methylmercury by solar radiation.

Methylmercury [MeHg(I) in the aerobic surface water of lakes is thought to be rapidly degraded, but contrary to expectations, we show that MeHg(I) concentrations often increase during sunlight hours or remain relatively constant. We hypothesized that there were water column processes that generated MeHg(I) and that these processes were linked to dissolved organic matter (DOM) and solar radiation. A 2-day diurnal pattern of MeHg(I) in surface water with corresponding bottled controls was assessed for two contrasting lakes in Kejimikujik, Nova Scotia, Canada. Following this study, a tangential ultrafiltrator was used to size-fractionate and generate a concentration gradient of DOM from four different lakes located near Lac Berthelot, Quebec, Canada. The watersheds of two of these lakes were not substantially logged whereas the other two had been extensively logged. Different size fractions of DOM as well as different concentrations of DOM were exposed to sunlight for varying periods of time. We observed that, in Keiimikujik, the concentration of MeHg(I) in surface waters peaked in the early afternoon. Furthermore, this also occurred in bottled water for one of the lakes, Puzzle, eliminating the possibility that in-lake mixing played a role in this pattern. The formation of MeHg(I) was found to be dependent on the size fraction and amount of DOM present in the water. Specifically, DOM less than 5 kDa or between 30 and 300 kDa generated MeHg(I) when exposed to sunlight, but larger fractions did not. Furthermore, although data are limited, we found that water from lakes with logged watersheds generated MeHg(I) when exposed to sunlight, whereas water from lakes with low levels of logging in the undisturbed watersheds did not. Our results demonstrate that MeHg(I) can be formed in freshwaters of certain lakes in response to solar radiation. This photoproduction of MeHg(I) is dependent on DOM concentrations and type, with the importance of water chemistry not yet clear. The significance of this process to freshwater lakes and the mechanism responsible for MeHg(I) photoproduction is still unclear, but a correction in the conventional wisdom that MeHg(I) is rapidly photodegraded is timely.

Animals↗

Photodegradation of phosmet in wool wax models and on sheep wool: determination of wool wax bound phosmet by means of isotope ratio mass spectrometry.

The photochemical reactions of phosmet, an organophosphorus insecticide used for plant protection and for control of ectoparasites on productive livestock, were studied in the presence of wool wax. Induced by UV light, phosmet features numerous degradation pathways as well as photoaddition reactions with lipid structure moieties. In model irradiation experiments of phosmet in mixtures of solvents (cyclohexane, cyclohexene, 2-propanol) and fatty acid methyl esters (methyl stearate, methyl oleate, 12-hydroxymethyl stearate), both adjusted to the hydroxyl and iodine values of wool wax, half-lives were determined to be approximately 7 and 16 h, respectively. Irradiation of phosmet on crude sheep wool resulted in a degradation rate of 65% after 24 h. In tracer studies with stable isotope labeled phosmet ([15N]phosmet) in commercial lanolin and on raw sheep wool, employing a sunlight simulator and natural sunlight, wool wax bound phosmet was formed. After extraction and measurement by elemental analyzer/isotope ratio mass spectrometry, delta15N values of the phosmet-free wool wax fractions were notably increased as compared to the value of natural lanolin. Calculated from the delta15N values, an average of 13.9/15.6% (sunlight simulator/natural sunlight) was bound to wool wax lipids after irradiation of thin films of commercial lanolin. In experiments with sheep wool, 13.2 and 15.4%, respectively, were detected as wax-bound.

Animals↗