Detection of iodine monoxide radicals in the marine boundary layer using laser induced fluorescence spectroscopy

A Laser Induced Fluorescence (LIF) instrument has been developed to detect iodine monoxide (IO) radicals in the atmosphere. An all solid-state Nd:YAG pumped Ti:Sapphire laser operating at approximately 445 nm was used to excite the (2,0) band of the IO A²Π_3/2 ← X²Π_3/2 electronic transition, with off-resonance fluorescence in the (2,5) band detected at 521 nm. The sensitivity of the instrument was determined by calibration. IO (between 10 and 150 pptV) was generated following the 184.9 nm photolysis of N₂O/CF₃I/N₂ mixtures with O₃ actinometry used to determine the photolysis flux. The detection limit was determined to be 0.3 pptV for a 300 s integration period, with an uncertainty of 23% (1σ). The instrument was deployed in August/September 2006 during the RHaMBLe (Reactive Halogens in the Marine Boundary Layer) campaign in Roscoff, France. Located on a small jetty, a few metres from the water’s edge at high tide, the instrument measured significant levels of IO on 11 days, with a maximum of 27.6 ± 3.2 pptV observed on one day (averaged over 10 s) representing the highest IO mixing ratio recorded in the marine boundary layer to date. IO displayed a clear diurnal profile with a maximum at low tide during the daytime. These results represent the first point measurements of IO in the atmosphere by LIF.     

Pollution Transport in the Southwest Pacific

The impacts of long range transport of pollutants from anthropogenic and natural sources play a major role in atmospheric chemistry and may have an impact on global climate change. Although atmospheric transport in the Northern Hemisphere is recognised as an essential feature on aglohalscale, longrange transport in the Southern Hemisphere may have important regional implications.     

Anthropogenic impacts on the water and salt budgets of St Lucia estuarine lake in South Africa

Lake St Lucia in South Africa is part of a UNESCO World Heritage site and a Ramsar wetland of international importance. Like many coastal wetlands worldwide, anthropogenic activities including catchment land-use changes, water diversions/abstractions, and manipulation of the mouth state have significantly affected its functioning over the past century. Questions concerning its sustainability have motivated a re-evaluation of management decisions made in the past and of options for the future. A model for the water and salt budgets has therefore been used to investigate “what if” scenarios in terms of past anthropogenic interventions. In particular, simulations allow us to evaluate the effects of diverting the Mfolozi river from St Lucia on the functioning of the system and on the occurrence of various water level/salinity states that drive the biological functioning of the ecosystem. In the past, when the St Lucia estuary and the Mfolozi river had a combined inlet, the mouth was predominantly open. The lake had relatively stable water levels but variable salinities that increased during dry conditions due to evaporative losses and saltwater inflows from the sea. If the mouth closed, the Mfolozi flow was diverted into the lake which reduced salinities and maintained or increased water levels. Simulations indicate that without a link to the Mfolozi the lake system would naturally have a mainly closed inlet with lower average salinities but more variable water levels. During dry conditions water levels would reduce and result in desiccation of large areas of the lake as has recently occurred. We conclude that the artificial separation of the St Lucia and Mfolozi inlets underpins the most significant impacts on the water & salt budget of the lake and that its reversal is key to the sustainability of the system.     

Effect of wave amplitude on turbulent flow in a wavy channel by direct numerical simulation

The present study numerically investigates the characteristics of three-dimensional turbulent flow in a wavy channel. For the purpose of a careful observation of the effect of the wave amplitude on the turbulent flow, numerical simulations are performed at a various range of the wave amplitude to wavelength ratio (0.01?α/λ?0.05), where the wavelength is fixed with the same value of the mean channel height (H). The immersed boundary method is used to handle the wavy surface in a rectangular grid system, using the finite volume method. The Reynolds number (Re=U_bH/ν) based on the bulk velocity (U_b) is fixed at 6760. The present computational results for a wavy surface are well compared with those of references. When α/λ=0.02, the small recirculating flow occurs near the trough at the instant, but the mean reverse flow is not observed. In the mean flow field, the reverse flow appears from α/λ=0.03 among the wave amplitude considered in this study. The domain of the mean reverse flow defined by the locations of separation and reattachment depends strongly on the wave amplitude. The pressure drag coefficient augments with increasing the wave amplitude. The friction drag coefficient shows the increase and decrease behavior according to the wave amplitude. The quantitative information about the flow variables such as the distribution of pressure and shear stress on the wavy surface is highlighted.     

Partitioning of polycyclic aromatic hydrocarbons between water and particles compared to bioaccumulation in mussels: a harbour case

Water and particles from three sites located in Halifax Harbour, near and further away from combined municipal sewage effluents (CMSE) were analysed for parental and alkylated polycyclic aromatic hydrocarbons (par and alkPAH). Bioavailability of PAH was compared for inter-tidal mussels collected at the same sites in April and November. The PAH fingerprint determined over 9 sampling times covering a period of 19 months differed more between phases (water and particles) and seasons, than between sites. In the spring, more alkPAH associated with diesel and gasoline were detected in the soluble phase, along with more bioaccumulation of alkPAH in inter-tidal mussels. A broader number of parPAH were detected in mussels collected in the fall. The mean sum of dissolved alkPAH concentrations was higher in water at the site closer to raw CMSE than at the other two sites and particles of that site. However, lowest bioconcentration factors (BCF) were determined in mussels of this more contaminated site. Similar biota-particle accumulation factors (BPAF) were determined for parPAH in mussels from the three sites, all lower than the BCF of alkPAH. The study indicates that sewage treatment plants will reduce the amount of parPAH especially larger than fluoranthene and pyrene from being deposited in the harbour; that alk naphthalenes and fluorenes present in water will continue to be discharged; that the disturbance of sediments can make particle-bound PAH available to mussels.     

The estimation of acid dissociation constants in seawater media from potentionmetric titrations with strong base. I. The ionic product of water — Kw

The various assumptions implicit in the calculation of acid dissociation constants (based on ionic medium standard states) from potentiometric titrations using a cell with liquid junction (i.e. a pH measuring cell) have been examined. It was concluded that results can be obtained having an accuracy commensurate with the experimental precision. It has been shown that although the precise composition of the medium is a function of the hydrogen ion concentration (because of the protolytic nature of some of the ions in the media, e.g., sulphate and fluoride), the effect of such variations in the medium composition can be compensated for when defining the activity of hydrogen ion on an ionic medium standard state by defining the concentration of hydrogen ion as:

where β_HSO4 and β_HF are the relevant association constants and S_T and F_T are the total concentrations of sulphate and fluoride, respectively.This approach was used to obtain values for the ionic product of water (K_W) in artificial seawater media at various temperatures and ionic strengths. These were fitted to give the equation (molal concentration units):

$\text{pK}{}_{\mathrm{w}}\text{=}\text{3441.0}\text{T}\text{+2.256-0.7091}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(}\text{rms deviation 0.01}\text{)}$

where I is the formal ionic strength of the artificial seawater medium and T is the absolute temperature. The values obtained are in reasonable agreement with those found by previous workers.     

The salt composition of rivers in Wrangel Island

Pioneer information about the chemical composition of river water in Wrangel Island has been obtained. It is shown that the water composition reflects the lithogeochemical specifics of primary rocks and ore mineralization. In contrast to many areas of the Russian Far North, river waters of the island are characterized by an elevated background value of total mineralization (i.e., total dissolved solids, TDS) (0.3–2 g/l) and specific chemical type (SO₄-Ca-Mg). This is related to abundance of Late Carboniferous gypsiferous and dolomitic sequences in the mountainous area of the island. It has also been established that the salt composition of some streams is appreciably governed by supergene alterations of the sulfide mineralization associated with the quartz-carbonate vein systems. They make up natural centers of surface water contamination. Waters in such streams are characterized by low pH values (2.4–5.5), high TDS (up to 6–23 g/l) and the SO₄-Mg composition. These waters are also marked by anomalously high concentrations of heavy and nonferrous metals, as well as REE, U, and Th.