Photochemical consequences of prolonged hydrological drought: A model assessment of the Lower Lakes of the Murray-Darling Basin (Southern Australia).

The prolonged "Millennium" drought affecting Australia in the 2000s had important consequences on surface-water bodies, including the Lower Lakes (Lake Alexandrina and Lake Albert) located at the terminal end of the River Murray system. Shallower water depths, limited solute dilution and altered geochemical processes ensured that the concentration values of several water constituents increased considerably during drought, including the water parameters of photochemical significance (nitrate, bicarbonate, carbonate and the dissolved organic carbon, DOC). The aim of this study was to model the photochemical processes in the Lower Lakes during the drought and post-drought periods, to provide insight into the changes that photoinduced reactions can undergo in periods of water scarcity. Among the photochemical processes involved in the light-assisted transformation of dissolved compounds, an important role is played by indirect photochemistry where degradation is triggered by photogenerated transient species such as hydroxyl (OH) and carbonate (CO3-) radicals, and the triplet states of chromophoric dissolved organic matter (3CDOM*). Results of photochemical modelling suggest that the reactions induced by 3CDOM* would be enhanced during drought, while the processes triggered by OH and CO3- would be less modified. For compounds undergoing efficient degradation with 3CDOM*, enhanced photochemistry during drought could offset the higher concentration values resulting from lower dilution. In contrast, for compounds mainly degraded by OH or CO3- the drought period could produce a concentration increase not balanced by an increment in the photochemical reactivity of the water body.

[A Method Based on Ru(bpy)3 3+ Electrogenerated Chemiluminescence for Assessment of Antioxidant Property of Naturally Occurring Antioxidants].

We developed a flow injection analysis (FIA) method based on tris(2,2'-bipyridine)ruthenium(III) [Ru(bpy)3 3+] electrogenerated chemiluminescence for assessment of antioxidant property. The hydroxyl radical (∙OH) were generated by H2O photolysis using an ultraviolet/H2O photoreactor. The reactor comprised a polytetrafluoroethylene tube, a quartz container, and a low-pressure mercury lamp that predominantly emitted radiation at around 185 nm. When the hydroxyl radical and Ru(bpy)3 3+ were in contact, chemiluminescence was generated as background emission. The background emission decreased when antioxidant samples were injected to the system. The antioxidant property of the naturally occurring antioxidants tested are listed herein, starting with the highest: gallic acid>ascorbic acid>quercetin. Moreover, our method allowed a sample throughput of approximately 100 samples/h. The proposed high throughput method can be used to assess the antioxidant property of the naturally occurring antioxidants.

The effectiveness of clove extracts in the inhibition of hydroxyl radical oxidation-induced structural and rheological changes in porcine myofibrillar protein.

Oxidation is a major cause of protein quality deterioration during the storage and processing of food. This study investigated the effects of clove extract (CE) on structural and rheological changes in porcine longissimus myofibrillar proteins (MP) and the effects of oxidizing radicals produced by a Fenton reaction system (FRS). Increased oxidation time was accompanied by increased carbonyl content, reduced Ca-ATPase activity, decreased enthalpy of denaturation, decreased thermal transition temperatures (P<0.05), and increased protein susceptibility to thermal aggregation. The addition of CE significantly inhibited carbonyl formation (P<0.05), enhanced solubility and thermal stability, and improved the gel formation ability (storage modulus, loss modulus) of MP. The protective effect of CE on protein denaturation was demonstrated by its efficacy in maintaining Ca-ATPase activity and decreasing the degree of protein aggregation. Overall, the hydroxyl radical-induced loss of the structural and functional properties of MP was significantly reduced by the presence of CE.

Risk assessment of marine environments from ballast water discharges with laboratory-scale hydroxyl radicals treatment in Tianjin Harbor, China.

For the majority of ballast water treatment system (BWTS) that employ active substances (e.g., oxidative compounds), relevant chemicals (RCs) formation is an issue owing to their potential adverse effects on aquatic organisms. Accordingly, BWTS must be approved by the International Maritime Organization (IMO), and the approval procedure requires environmental risk assessment. The most commonly employed harbor used to calculate predicted environmental concentrations (PECs) for RCs in treated ballast water is the GESAMP-BWWG (Group of Experts on Scientific Aspects of Marine Environmental Protection-Ballast Water Working Group) model harbor. However, there is very little assessment data available regarding the associated environmental impacts in ports and harbors of China. Therefore, in this study the concentration of fifteen RCs from the existing laboratory-scale BWTS using hydroxyl radicals was obtained and input into the MAMPEC (Marine Antifoulant Model to Predict Environmental Concentrations) model to compute PECs in Tianjin Harbor, China. The potential risks to the aquatic environment posed by treated ballast water in Tianjin Harbor were further assessed based on the calculated ratio of PECs and predicted no effect concentrations (PNECs). Only monochloroacetic acid and dichloroacetic acid were found to have potential risks, and the ratios of PECs and PNECs to the other measured RCs were less than 1, indicating that the environmental risk posed by treated ballast water discharged into Tianjin Harbor is of little concern. The concentration of total residual oxidant recommended by the IMO (<0.2 mg/L) in treated ballast water at discharge was found to be at levels that may pose a risk to the aquatic environment in Tianjin Harbor.

A rapid and sensitive method for hydroxyl radical detection on a microfluidic chip using an N-doped porous carbon nanofiber modified pencil graphite electrode.

Hydroxyl radicals (˙OH) play an important role in human diseases. Traditional detection methods are time consuming and require expensive instruments. Here, we present a simple and sensitive method for the detection of hydroxyl radicals on a microfluidic chip using an electrochemical technique. Aniline monomer is electrochemically polymerized on the surface of a pencil graphite electrode and carbonized at 800 °C. The resulting N-doped porous carbon nanofiber-modified pencil graphite electrode is embedded into a microfluidic chip directly as a working electrode. 4-Hydroxybenzoic acid (4-HBA) is selected as the trapping agent owing to its unique 3,4-DHBA product and high trapping efficiency. A low detection limit of 1.0 × 10(-6) M is achieved on the microfluidic chip. As a demonstration, the microfluidic chip is successfully utilized for the detection of ˙OH in cigarette smoke. The strong π-π stacking and hydrophobic interactions between the nitrogen-doped carbon materials and the pencil graphite make the modified electrode well-suited for the microfluidic chip.

Modelling lake-water photochemistry: three-decade assessment of the steady-state concentration of photoreactive transients (·OH, CO3(-·) and (3)CDOM(∗)) in the surface water of polymictic Lake Peipsi (Estonia/Russia).

Over the last 3-4 decades, Lake Peipsi water (sampling site A, middle part of the lake, and site B, northern part) has experienced a statistically significant increase of bicarbonate, pH, chemical oxygen demand, nitrate (and nitrite in site B), due to combination of climate change and eutrophication. By photochemical modelling, we predicted a statistically significant decrease of radicals ·OH and CO3(-·) (site A, by 45% and 35%, respectively) and an increase of triplet states of chromophoric dissolved organic matter ((3)CDOM(∗); site B, by ∼25%). These species are involved in pollutant degradation, but formation of harmful by-products is more likely with (3)CDOM(∗) than with ·OH. Therefore, the photochemical self-cleansing ability of Lake Peipsi probably decreased with time, due to combined effects of climate change and eutrophication. In different environments (e.g. Lake Maggiore, NW Italy), ecosystem restoration policies had the additional advantage of enhancing sunlight-driven detoxification, suggesting that photochemical self-cleansing would be positively correlated with lake water quality.

Oxidation of organics in retentates from reverse osmosis wastewater reuse facilities.

The use of membrane processes for wastewater treatment and reuse is rapidly expanding. Organic, inorganic, and biological constituents are effectively removed by reverse osmosis (RO) membrane processes, but concentrate in membrane retentates Disposal of membrane concentrates is a growing concern. Applying advanced oxidation processes (AOPs) to RO retentate is logical because extensive treatment and energy inputs were expended to concentrate the organics, and it is cheaper to treat smaller flowstreams. AOPs (e.g., UV irradiation in the presence of titanium dioxide; UV/TiO(2)) can remove a high percentage of organic matter from RO retentates. The combination of AOPs and a simple biological system (e.g., sand filter) can remove higher levels of organic matter at lower UV dosages because AOPs produce biologically degradable material (e.g., organic acids) that have low hydroxyl radical rate constants, meaning that their oxidation, rather than that of the primary organic matter in the RO retentate, dictates the required UV energy inputs. At the highest applied UV dose (10 kWh m(-)3), the dissolved organic carbon (DOC) in the RO retentate decreased from approximately 40 to 8 mg L(-)1, of which approximately 6 mg L(-)1 were readily biologically degradable. Therefore, after combined UV treatment and biodegradation, the final DOC concentration was 2 mg L(-)1, representing a 91% removal. These results suggest that UV/TiO(2) plus biodegradation of RO retentates is feasible and would significantly reduce the organic pollutant loading into the environment from wastewater reuse facilities.

[Assessment of rate of hydroxyl anions production by Helicobacter pylori in stomach].

Production of hydroxyl anions by tissue samples of pylorus mucous membrane obtained from 45 patients with gastric or duodenal ulcers was investigated. The production was estimated using the recently developed method based on measurement of rate of pH change in urea-containing reaction mixture. The rate of [OH-] generation as a result of H. pylori metabolism accounted on pylorus square varied from 0.4 to 1318.9 mcmol [OH-]/min, and in 90.2% of cases it did not exceed 128.1 mcmol [OH-]/min. This rate is comparable to mean rate of [H+] generation in stomach of healthy man--114.2-238.4 mcmol [H+]/min. Obtained results allow to conclude that this bacterium may participate in regulation of stomach acid-base balance.