Modeling the photo-oxidation of dissolved organic matter by ultraviolet radiation in freshwater lakes: implications for mercury bioavailability

Uncertainties in projected ultraviolet (UV) radiation may lead to future increases in UV irradiation of freshwater lakes. Because dissolved organic carbon (DOC) is the main binding phase for mercury (Hg) in freshwater lakes, an increase in DOC photo-oxidation may affect Hg speciation and bioavailability. We quantified the effect of DOC concentration on the rate of abiotic DOC photo-oxidation for five lakes (DOC=3.27-12.3 mg L(-1)) in Kejimkujik National Park, Canada. Samples were irradiated with UV-A or UV-B radiation over a 72-h period. UV-B radiation was found to be 2.36 times more efficient at photo-oxidizing DOC than UV-A, with energy-normalized rates of dissolved inorganic carbon (DIC) production ranging from 3.8×10(-5) to 1.1×10(-4) mg L(-1)J(-1) for UV-A, and from 6.0×10(-5) to 3.1×10(-4) mg L(-1)J(-1) for UV-B. Energy normalized rates of DIC production were positively correlated with DOC concentrations. Diffuse integrated attenuation coefficients were quantified in situ (UV-A K(d)=0.056-0.180 J cm(-1); UV-B K(d)=0.015-0.165 J cm(-1)) and a quantitative depth-integrated model for yearly DIC photo-production in each lake was developed. The model predicts that, UV-A produces between 3.2 and 100 times more DIC (1521-2851 mg m(-2) year(-1)) than UV-B radiation (29.17-746.7 mg m(-2) year(-1)). Future increases in UV radiation may increase DIC production and increase Hg bioavailability in low DOC lakes to a greater extent than in high DOC lakes.     

The effects of UV exclusion on the soluble phenolics of young Scots pine seedlings in the subarctic

The characteristics of UV-absorbing compounds, particularly soluble phenolics, were studied in needles of 63-day-old seed-grown Scots pine (Pinus sylvestris L.) seedlings of two provenances in a UV exclusion field experiment at Pallas-Ounastunturi National Park in Finnish Lapland (68 degrees N, 270 m a.s.l.). The experiment used the following plastic filters in exclosure treatments to manipulate the spectral balance of natural irradiance: (1) 'control' (a polyethene plastic filter); (2) 'UV-B exclusion' (a clear polyester filter); and (3) 'UV-B/UV-A exclusion' (a clear acryl plate). Polyethene transmitted 89% of the ambient levels of total UV (280-400 nm), polyester transmitted 75% of the total UV, but only 0.6% of the UV-B (280-315 nm) component, while acryl plate transmitted 0.2% of UV (280-360 nm). The research also included (4) 'Ambient' plants that were not subjected to any treatment exclosures. After the 58 day UV exclusion, significant (p<0.0001) differences due to treatments were determined for a kaempferol derivative, kaempferol 3-glucoside, and a quercetin derivative, the quantities of which ranged from 0.23 to 0.45, 0.42 to 1.34 and 0.39 to 0.75 micromol g FW(-1), respectively, depending on treatment and provenance. Overall, Scots pine seedlings grown at ambient UV radiation (PAS300, Caldwell's generalized Plant Action Spectrum (PAS) normalized at 300 nm, 72 mW m(-2)) or under a control had significantly (p<0.05) higher quantities of soluble phenolics than seedlings grown under UV-B or UV-B/UV-A exclusion treatments. There were no significant differences in the quantity of soluble phenolics between the two exclosure treatments or between the two Scots pine provenances. The sums of diacylated flavonol glucosides ranging from 3.75 to 4.55 micromol g FW(-1) depending on treatment and provenance, were already present at very low UV-levels under the UV-B/UV-A exclusion treatment. The present study indicated that soluble phenolics, particularly the diacylated flavonol glucosides, may provide an effective preformed protection for young Scots pine seedlings against UV-B and UV-A radiation.     

Influence of solar UV radiation on the nitrogen metabolism in needles of Scots pine (Pinus sylvestris L.)

Needles of 20-year-old Scots pine (Pinus sylvestris L.) saplings were studied in an ultraviolet (UV) exclusion field experiment (from 2000 to 2002) in northern Finland (67 °N). The chambers held filters that excluded both UV-B and UV-A, excluded UV-B only, transmitted all UV (control), or lacked filters (ambient). UV-B/UV-A exclusion decreased nitrate reductase (NR) activity of 1-year-old needles of Scots pines compared to the controls. The proportion of free amino acids varied in the range 1.08-1.94% of total proteins, and was significantly higher in needles of saplings grown under UV-B/UV-A exclusion compared to the controls or UV-B exclusion. NR activity correlated with air temperature, indicating a “chamber effect”. The study showed that both UV irradiance and increasing temperature are significant modulators of nitrogen (N) metabolism in Scots pine needles.     

UV-light induced mineralization of organic matter bound chlorine in Lake Bjän,Sweden--a laboratory study

Surface water and aqueous solutions of isolated organic matter from a humic rich lake in southern Sweden were exposed to artificial UV radiation to investigate the UV light induced influence on organic matter bound chlorine in natural systems. It was found that the photodegradation of organic matter bound chlorine was more pronounced than the photodegradation of organic carbon. After 120 h of irradiation of the isolated organic matter, only 35% of the initial organochlorine was still in the solution compared to about 70% of the dissolved organic carbon (DOC). A similar result was obtained for unfractionated surface water. Furthermore, our results indicate that the loss of organic chlorine was mainly due to a mineralization of organic chlorine into chloride ions. The total decrease of organic chlorine after 120 h was 32 microg Cl(org) l(-1), of which the major part disappeared in the initial irradiation phase. A similar increase was observed in the chloride concentration (34 microg Cl(-) l(-1)).     

Photoinduced toxicity of retene to Daphnia magna under enhanced UV-B radiation

The effects of UV radiation on the acute toxicity of retene (7-isopropyl-1-methylphenanthrene) to Daphnia magna Straus were studied. Dehydroabietic acid (DHAA) from which retene is formed in the vicinity of pulp and paper industry was also studied. Pyrene, anthracene, and phenanthrene were used as model PAH compounds. The time taken for immobilization (ET50) was monitored under biologically effective UV-B dose rates of 240, 365, 565, and 650 mW m(-2) (UV-A and visible light also present). Median effective concentrations (EC50) were determined after a 15-min UV exposure (565 mW m(-2)) followed by 24 h in the dark. Retene (10-320 microg l(-1)) was not acutely toxic in the dark. The induction of phototoxicity was in agreement with the absorption properties of the compounds (absorption peak of retene at around 300 nm). Photoinduced toxicity followed an order pyrene > anthracene > retene. Phenanthrene and DHAA were not acutely phototoxic. Accumulation of the compound in Daphnia before UV exposure was essential. Some changes in the absorption spectra of the compounds were seen after a 5-h UV irradiation (565 mW m(-2)), but none of the irradiated compounds were acutely toxic without further UV exposure. Therefore, the enhanced acute toxicity was primarily due to internal photosensitization reactions rather than photomodification. The dissolved fraction of 25% pulp and paper mill effluent reduced phototoxicity by attenuating UV radiation. The phototoxicity of retene was a function of both the exposure concentration and the UV-B dose rate, but relatively high UV-B dose rates and concentrations were needed for the acute photoinduced toxicity.     

Occurrence of UV filter compounds from sunscreens in surface waters: regional mass balance in two Swiss lakes

Consumer care products often contain UV filters, organic compounds which absorb ultraviolet light. These compounds may enter surface waters directly (when released from the skin during swimming and bathing) or indirectly via wastewater treatment plants (when released during showering or washed from textiles). Predicted and measured UV filter concentrations were compared in a regional mass balance study for two Swiss lakes: Lake Zurich, a typical midland lake which is also an important drinking water resource, and Hüttnersee, a small bathing lake. Both lakes are extensively used for recreational activities and considerable direct input of UV filters is thus expected. This input was estimated from the number of visitors at swimming areas around the lakes and a survey of the usage of sunscreen products among these visitors. Possible additional indirect input via wastewater treatment plants was not considered in this study. The quantitatively most important UV filters, as indicated by the survey data, ethylhexyl methoxycinnamate, octocrylene, 4-methylbenzylidene camphor, butyl methoxydibenzoylmethane, and benzophenone-3, all lipophilic compounds, were selected for analysis by gas chromatography-mass spectrometry. Concentrations of individual UV filters in water from Lake Zurich were low, ranging from <2 ng l(-1) (detection limit) to 29 ng l(-1), and somewhat higher at Hüttnersee, ranging from <2 to 125 ng l(-1), with the highest concentrations found in summer, consistent with direct inputs to the lakes during this time. The concentrations were clearly lower than predicted from input estimates based on the surveys. This may be in part due to (i) an overestimation of these inputs (e.g. less than the 50% wash-off of UV filters assumed to occur during swimming), and (ii) some removal of these compounds from the lakes by degradation and/or sorption/sedimentation. UV filters were also detected in semipermeable membrane devices (SPMDs) deployed at Lake Zurich and Greifensee, another midland lake, at concentrations of 80-950 ng SPMD(-1), confirming the presence of the compounds in surface waters and indicating a certain potential for bioaccumulation. SPMD-derived water concentrations were in the range of 1-10 ng l(-1) and thus corresponded well with those determined in water directly. No UV filters were detected above blank levels in SPMDs deployed at a remote mountain lake used for background measurements.     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Effects of ultraviolet-B radiation (UV-B) on growth and physiology of the dune grassland species Calamagrostis epigeios

Seedlings of Calamagrostis epigeios were exposed to four levels of UV-B radiation (280-320 nm), simulating up to 44% reduction of stratospheric ozone concentration during summertime in The Netherlands, to determine the response of this plant species to UV-B irradiation. After six weeks of UV-B treatment, total biomass of all UV-B treated plants was higher, compared to plants that had received no UV-B radiation. The increase of biomass did not appear to be the result of a stimulation of net photosynthesis. Also, transpiration rate and water use efficiency were not altered by UV-B at any exposure level. Pigment analysis of leaf extracts showed no effect of enhanced UV-B radiation on chlorophyll content and accumulation of UV absorbing pigments. UV-B irradiance, however, did reduce the transmittance of visible light (400-700 nm) of intact attached leaves, suggesting a change in anatomical characteristics of the leaves. Additionally, the importance of including an ambient UV-B treatment in indoor experiments is discussed.     

The degradation of the cyanobacterial hepatotoxin nodularin (NOD) by UV radiation

This study investigates the decomposition of NOD by UV irradiation. Water solutions of pure NOD and NOD-containing Nodularia extract as well as Nodularia filaments collected on filters were exposed to UV-A, UV-B, and white fluorescent light (VIS) during 48 h experiments. In VIS, the toxin was fairly stable and only 3.8-4.6% of the original degraded. UV-B had the most pronounced effect on the NOD degradation rate. In the experiment, the overall loss of NOD was 0.27 and 0.77 micro g ml(-1)day(-1) for the solution of pure toxin and Nodularia extract and 0.28 micro g day(-1) for Nodularia filaments. Comparison of UV-B degradation rate in water and methanol extracts revealed higher stability of NOD in methanol. This might suggest that some hydrophobic components of Nodularia cell play a protective role against UV radiation. Additionally, chemical (LC-MS/MS) and biochemical (ELISA and PPIA) assays were employed to characterize the UV degradation products. LC-MS/MS analyses showed that in UV-B exposed sample, apart from NOD, there were three other compounds with molecular ion at m/z at 825.4. The fragmentation pattern of the ion was the same for all four compounds suggesting that they are geometrical isomers of NOD. The major degradation product, with a local absorption maximum at 242 nm, was active in both biochemical assays.     

Influence of natural dissolved organic carbon on the bioavailability of mercury to a freshwater alga

Bioavailability of mercury (Hg) to Selenastrum capricornutum was assessed in bioassays containing field-collected freshwater of varying dissolved organic carbon (DOC) concentrations. Bioconcentration factor (BCF) was measured using stable isotopes of methylmercury (MeHg) and inorganic Hg(II). BCFs for MeHg in low-DOC lake water were significantly larger than those in mixtures of lake water and high-DOC river water. The BCF for MeHg in rainwater (lowest DOC) was the largest of any treatment. Rainwater and lake water also had larger BCFs for Hg(II) than river water. Moreover, in freshwater collected from several US and Canadian field sites, BCFs for Hg(II) and MeHg were low when DOC concentrations were >5mg L(-1). These results suggest high concentrations of DOC inhibit bioavailability, while low concentrations may provide optimal conditions for algal uptake of Hg. However, variability of BCFs at low DOC indicates that DOC composition or other ligands may determine site-specific bioavailability of Hg.     

太阳光对湖泊中有机污染物降解的研究进展

论述了太阳光对湖泊水体中有机污染物降解作用的研究,就其降解机理、动力学特征、作用对象及降解产物等作了逐一介绍.阐明了太阳光对生物降解湖泊水体中有机污染物具有协同作用,也概述了光降解作用受pH、溶解性有机物(DOM)、水深与水体运动、地理、水文、水质与气候等因素的影响.并对实验室模拟条件下的降解与自然条件下的降解进行对比,提出今后该领域的发展前景与研究方向.     

Alkaline hydrolysis of humic substances--spectroscopic and chromatographic investigations.

To find out more on the structure of humic substances (HS), isolated dissolved organic carbon (DOC) samples from a brown water lake and a wastewater effluent were fractionated and subjected to alkaline hydrolysis. UV/Vis and fluorescence spectroscopy, as well as size-exclusion chromatography with on-line detection of UV absorption, fluorescence and DOC concentration were used to investigate the structural changes caused by the hydrolysis reaction. Following hydrolysis, the fluorescence intensity increased considerably despite a decrease in the UV absorption. The UV absorption and the DOC data from the SEC experiments revealed a strong shift to smaller molecular sizes after hydrolysis. The spectra of the hydrolysed samples, as well as the size-exclusion chromatograms, were compared to spectra of hydroxybenzoic acids and hydroxycinnamic acids. From this comparison, it can be concluded that the hydrolysis products have a structure similar to these organic acids.     

Long-term exposure to enhanced UV-B radiation has no significant effects on growth or secondary compounds of outdoor-grown Scots pine and Norway spruce seedlings

The effects of long-term enhanced UV-B radiation on growth and secondary compounds of two conifer species were studied in an outdoor experiment. Scots pine (Pinus sylvestris) seedlings were exposed for two growing seasons and Norway spruce (Picea abies) seedlings for three growing seasons to supplemental UV-B radiation, corresponding to a 30% increase in ambient UV-B radiation. The experiment also included appropriate controls for ambient and increased UV-A radiation. Enhanced UV-B did not affect the growth of the conifer seedlings. In addition, neither the concentrations of terpenes and phenolics in the needles nor the concentrations of terpenes in the wood were affected. However, in the UV-A control treatment the concentrations of diterpenes in the wood of Scots pine decreased significantly compared to the ambient control. Apparently, a small increase in UV-B radiation has no significant effects on the secondary compounds and growth of Scots pine and Norway spruce seedlings.     

Decolorizing of lignin wastewater using the photochemical UV/TiO2 process

Studies on applying the photochemical UV/TiO2 oxidation process to treat the lignin-containing wastewater for dissolved organic carbon (DOC), color and reducing A254 (the absorption at the wavelength of 254 nm) have been carried out. The data obtained in this study demonstrate that the UV/TiO2 process is effective in oxidizing the lignin thus reducing the color and DOC of the wastewater treated. The combined UV/TiO2 treatment can achieve better removal of DOC and color than the UV treatment alone. Color removal, based on American Dye Manufacture Index (ADMI) measurement, is greater than 99% if the pH is maintained at 3.0 with the addition of 1 g l(-1) TiO2. When 10 g l(-1) TiO2 is applied, the oxidation reduction potential (ORP) value is reached to result in an 88% removal of both DOC and color. A model was developed based on the variation of ORP during the photochemical reaction to simulate the decoloring process. The proposed model can be used to predict the color removal efficiency of the UV/TiO2 process.     

Towards a model of acidification effects on waterfowl in Eastern Canada

Data from 212 lakes in central Ontario were used to examine the relationship between presence of breeding waterfowl and loons and the following lake characteristics: pH, presence of fish, lake area, dissolved organic carbon (DOC) and total phosphorus (TP) concentration. In univariate analyses, the two fish-eating species preferred large, high pH lakes with fish, while insectivorous species showed little consistent pattern of lake association. Logistic regression analyses confirmed that large lake size and presence of fish were important determinants of presence of piscivores, though the residual effect of pH differed between the two species. Broods of three of the four insectivorous species avoided lakes with fish, and independently showed a positive response to pH. By calculating the probability that fish will be present on a lake of given area and pH, it is possible to estimate the net effect of pH change on these waterfowl. Relationships such as those presented here can, with some assumptions, be linked to models of lake acidification to estimate response of waterfowl to predicted changes in acidic deposition.     

Attempts to probe the ozone layer and the ultraviolet-B levels of the past

To get a proper perspective on the current status of atmospheric ozone, which protects the biosphere from ultraviolet-B (UV-B; 280-315 nm) radiation, it would be of value to know how ozone and UV-B radiation have varied in the past. The record of worldwide ozone monitoring goes back only a few decades, and the record of reliable UV-B measurements is even shorter. Here we review indirect methods to assess their status further back in time. These include variations in the Sun's emission and how these affect the atmosphere, changes in the Earth's orbit, geologic imprints of atmospheric ozone, effects of catastrophic events such as volcanic eruptions, biological proxies of UV-B radiation, the spectral signature of terrestrial ozone in old recordings of star spectra, and the modeling of UV-B irradiance from ozone data and meteorological recordings. Although reliable reconstructions do not yet extend far into the past, there is some hope for future progress.     

An empirical method for the conversion of spectral UV irradiance measurements to actinic flux data

Routinely monitored radiation parameters, including those at UV wavelengths, most commonly refer to irradiance, that is the radiation incident on a flat horizontal plate. However, in the study of atmospheric chemistry, where UV radiation is a prime photochemical driver, the target molecules are approximately spherical and the actinic flux (radiation on the surface of a sphere) is a better measure of the effective radiation. Unfortunately actinic flux measurements (also known as scalar irradiance) are uncommon research measurements. The ability to convert irradiance data to actinic flux data within a reasonable degree of uncertainty would provide an actinic flux database mapped from existing irradiance databases, thus vastly increasing knowledge of actinic flux variability and climatology. Synchronised spectral UV irradiance and actinic flux measurements have been made during the ADMIRA project, and used to develop an empirical method for converting irradiance to actinic flux. With some prior knowledge of the sky conditions during the irradiance measurements the actinic flux can be estimated to within a few percent. If no knowledge of the sky conditions is available then the empirical method still returns actinic fluxes within 10% of those measured at the site for which the conversion was developed.     

UV-B radiation and acclimation in timberline plants

Research has shown that some plants respond to enhanced UV-B radiation by producing smaller and thicker leaves, by increasing the thickness of epidermis and concentration of UV-B absorbing compounds of their surface layers and activation of the antioxidant defence system. The response of high-altitude plants to UV-B radiation in controlled conditions is often less pronounced compared to low-altitude plants, which shows that the alpine timberline plants are adapted to UV-B. These plants may have a simultaneous co-tolerance for several stress factors: acclimation or adaptation to the harsh climate can also increase tolerance to UV-B radiation, and vice versa. On the other hand, alpine timberline plants of northern latitudes may be less protected against increasing UV-B radiation than plants from more southern latitudes and higher elevations due to harsh conditions and weaker preadaptation resulting from lower UV-B radiation exposure. It is evident that more long-term experimental field research is needed in order to study the interaction of climate, soil and UV-B irradiance on the timberline plants.     

Factors affecting population fluctuations of the glacial relict amphipod Monoporeia affinis (Lindström) in Sweden's largest lakes

Factors affecting long-term (1982-2000) population densities of the glacial relict amphipod Monoporeia affinis were studied in Sweden's three largest lakes. Monoporeia showed large population fluctuations in all three lakes, with conspicuous peaks in density occurring in Lakes V?nern and M?laren. In Lake V?nern, amphipod densities showed highly significant relationships with spring maximum diatom biovolume at a 1-yr lag. The lack of relationship between diatom biovolumes and Monoporeia densities in L. V?ttern is likely due to the larger depth and the lower nutrient content of this lake. In eutrophic L. M?laren, summer hypoxia (< 4 mg O2 L-1) is likely an important regulating factor. Hypolimnetic temperature showed a clear periodicity with relatively warm deep water occurring between 1989 and 1994. Hypolimnetic temperatures in V?nern and V?ttern were correlated with total solar irradiance. However, neither hypolimnetic water temperature nor diatom biovolumes correlated with the North Atlantic Oscillation winter index. We speculate that variations in temperature and near-bottom oxygen concentrations negatively affect population densities by acting on recruitment success (reproduction) and juvenile (young-of-the-year) survival.     

Effects of pre-exposure to ultraviolet-B radiation on responses of tomato (Lycopersicon esculentum cv. New Yorker) to ozone in ambient and elevated carbon dioxide

Patterns of environmental change in the biosphere include concurrent and sequential combinations of increasing ultraviolet (UV-B) and ozone (O(3)) at increasing carbon dioxide (CO(2)) levels; long-term changes are resulting mainly from stratospheric O(3) depletion, greater tropospheric O(3) photochemical synthesis, and increasing CO(2) emissions. Effects of selected combinations were evaluated in tomato (Lycopersicon esculentum cv. New Yorker) seedlings using sequential exposures to enhanced UV-B radiation and O(3) in differential CO(2) concentrations. Ambient (7.2 kJ m(-2 )day(-1)) or enhanced (13.1 kJ m(-2) day(-1)) UV-B fluences and ambient (380 microl l(-1)) or elevated (600 microl l(-1)) CO(2) were imposed for 19 days before exposure to 3-day simulated O(3) episodes with peak concentrations of 0.00, 0.08, 0.16 or 0.24 microl l(-1) O(3) in ambient or elevated CO(2). CO(2) enrichment increased dry mass, leaf area, specific leaf weight, chlorophyll concentration and UV-absorbing compounds per unit leaf area. Exposure to enhanced UV-B increased leaf chlorophyll and UV-absorbing compounds but decreased leaf area and root/shoot ratio. O(3) exposure generally inhibited growth and leaf photosynthesis and did not affect UV-absorbing compounds. The highest dose of O(3) eliminated the stimulating effect of CO(2) enrichment after ambient UV-B pre-exposure on leaf photosynthesis. Pre-exposure to enhanced UV-B mitigated O(3) damage to leaf photosynthesis at elevated CO(2).