An Assessment of the Performance of the PLUS+ Tool in Supporting the Evaluation of Water Framework Directive Compliance in Scottish Standing Waters.

Phosphorus is one of the main causes of waterbodies in Scotland being at less than good ecological status (GES) in terms of the water framework directive (WFD). In Scotland, there are more than 8000 standing waters, defined as lakes and reservoirs that have a surface area of more than 0.5 km2. Only about 330 of these are monitored routinely to assess compliance with the WFD. The export coefficient tool PLUS+ (phosphorus land use and slope) has been developed to estimate total phosphorus (TP) concentrations in the unmonitored sites; modelled values are then compared to WFD target concentrations for high, good, moderate, poor, and bad status to assess compliance. These type-specific or site-specific targets are set by the regulatory authority and form part of a suite of physical, chemical, and ecological targets that are used to assess GES, all of which must be met. During development, the PLUS+ tool was applied to 323 monitored catchments and 7471 unmonitored catchments. The efficacy of the tool was assessed against TP concentrations observed in 2014 and found to perform well in the rural catchments. 51% of standing waters had the same modelled and observed WFD class (i.e., High, Good, Moderate, Poor, Bad), and a further 40% of standing waters had a modelled WFD class that was within one class of observed water quality. The tool performed less well in catchments with larger inputs of TP from urban sources (e.g., sewage). The greatest deviations between measured and modelled classes were explained by the shortage of information on wastewater treatment works, fish farms, migratory birds, levels of uncertainty in TP measurements, and the amount of in-lake re-cycling of P. The limitations of the tool are assessed using data from six well documented case study sites and recommendations for improving the model performance are proposed.

Synthesis, properties, and photodynamic properties in vitro of heavy-chalcogen analogues of tetramethylrosamine.

Thio and seleno analogues of tetramethylrosamine were prepared by the directed-metalation/cyclization of the corresponding N,N-diethyl 2-(3-dimethylaminophenylchalcogeno)-4-dimethylaminobenzamide to the 2,7-bis-(N,N-dimethylamino)-9H-chalcogenoxanthen-9-one followed by the addition of phenylmagnesium bromide, dehydration, and ion exchange to the chloride salt. The thio and seleno tetramethylrosamines had longer wavelengths of absorption and higher quantum yields for the generation of singlet oxygen than tetramethylrosamine. Both the thio and selenoanalogues of tetramethylrosamine were efficient photosensitizers against R3230AC rat mammary adenocarcinoma cells in vitro.

Selenoxanthones via directed metalations in 2-arylselenobenzamide derivatives.

The reaction of N, N-diethyl 4-(N', N'-dimethylamino)-2-phenylselenobenzamide (7a), N, N-diethyl 4-methoxy-2-phenylselenobenzamide (7b), N, N-diethyl 4-(N', N'-dimethylamino)-2-[(3-(N, N-dimethylamino)phenylseleno]benzamide (7c), and N, N-diethyl 4-methoxy-2-(3-methoxyphenylseleno)-benzamide (7d) with excess lithium diisopropylamide (LDA) gave 2-N, N-(dimethylamino)-9H-selenoxanthone (9a), 2-methoxy-9H-selenoxanthone (9b), 2,7-bis-N, N-(dimethylamino)-9H-selenoxanthone (9c), and 2,5-dimethoxy-9H-selenoxanthone (9d) in 70%, 59%, 23%, and 90% isolated yields, respectively. N, N-Diethyl 2-phenylselenobenzamide (2-Se) gave no reaction with LDA, t-BuLi, MeLi, or lithium 2,2,6,6-tetramethylpiperidide as base. Electron donation from the 4-substituent of benzamide derivatives 7a-7d may increase the directing ability of the carbonyl oxygen to metalate the 2-position of the arylseleno group.