Oxidation of Volatile Organic Compounds in Aqueous Solution and at the Air-water Interface of Aqueous Microdroplets

Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.

During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H₂O₂ in dilute ISO solutions. This process yields C₁₀H₁₅OH species as primary products, whose formation both requires and is inhibited by O₂. Several isomers of C₁₀H₁₅OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH⁺ (m/z = 153) and MH⁺-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O₂) leading to second generation HO(ISO)₂· radicals that terminate as C₁₀H₁₅OH via β-H abstraction by O₂.

It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.

In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl₂ solutions simultaneously exposed to H₂O₂(g). Monomer and oligomeric species (ISO)1-8H⁺ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H⁺. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.

Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H₂O₂ were also carried out to test the surface oxidation of ISO(g) by photolyzing H₂O₂(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H⁺ at pH < 4, and new m/z⁺ = 271 and m/z^- = 76 products at pH > 5.

Arctic charr from Ennerdale water - relicts of the ice age

The work discussed in this report deals with aspects of the ecology of Arctic charr (Salvelinus alpinus, L.). The main aims of the study were: (1) To assess the relative abundance of migrants entering the River Liza and Smithy Beck in the English Lake District). (2) To assess the degree of stream specificity. (3) To determine the period of residency in the streams. (4) To obtain a better understanding of migratory behaviour. (5) To determine the growth rate of mature fish. (6) To determine the morphometric and meristic attributes. In conjunction with this work a study was carried out to investigate the feasibility of using a video recording system to monitor the migration of charr in Smithy Beck.

All their eggs in one basket: a rocky reef nursery for the longnose skate (Raja rhina Jordan & Gilbert, 1880) in the southern California Bight

Skates (family Rajidae) are oviparous and lay tough, thick-walled eggs. At least some skate species lay their eggs in spatially restricted nursery grounds where embryos develop and hatch (Hitz, 1964; Hoff, 2007). After hatching, neonates may quickly leave the nursery grounds (Hoff, 2007). Egg densities in these small areas may be quite high. As an example, in the eastern Bering Sea, a site <2 km2 harbored eggs of Alaska skate (Bathyraja parmifera) exceeding 500,000/km2. All skate nursery grounds have been identified over soft sea floors (Lucifora and García, 2004; Hoff, 2007).

Impact of the California sea lion (Zalophus californianus) on salmon fisheries in Monterey Bay, California

To assess the impact of California sea lions (Zalophus californianus) on salmon fisheries in the Monterey Bay region of California, the percentages of hooked fish taken by sea lions in commercial and recreational salmon fisheries were estimated from 1997 to 1999. Onboard surveys of sea lion interactions with the commercial and recreational f isheries and dockside interviews with fishermen after their return to port were conducted in the ports of Santa Cruz, Moss Landing, and Monterey. Approximately 1745 hours of onboard and dockside surveys were conducted—924 hours in the commercial fishery and 821 hours in the recreational fishery (commercial passenger fishing vessels [CPFVs] and personal skiffs combined). Adult male California sea lions were responsible for 98.4% of the observed depredations of hooked salmon in the commercial and recreational fisheries in Monterey Bay. Mean annual percentages of hooked salmon taken by sea lions ranged from 8.5% to 28.6% in the commercial fishery, 2.2% to 18.36% in the CPFVs, and 4.0% to 17.5% in the personal skiff fishery. Depredation levels in the commercial and recreational salmon fisheries were greatest in 1998—likely a result of the large El Niño Southern Oscillation (ENSO) event that occurred from 1997 to 1998 that reduced natural prey resources. Commercial fishermen lost an estimated $18,031−$60,570 of gear and $225,833−$498,076 worth of salmon as a result of interactions with sea lions. Approximately 1.4−6.2% of the available salmon population was removed from the system as a result of sea lion interactions with the fishery. Assessing the impact of a growing sea lion population on fisheries stocks is difficult, but may be necessary for effective fisheries management.

Competing for the Recreational Dollar: An Analysis of the California Commercial Passenger-Carrying Fishing Vessel Industry

California has a large and diverse marine recreational fishery. Anglers on commercial passenger-carrying fishing vessels (CPFV's) harvest a substantial proportion of California's marine recreational fisheries landings, accounting for about 40 percent and 16 percent of the total 1986 marine recreational catch in southern and northern California, respectively (NMFS, 1987). In 1986, 459,369 CPFV anglers landed some 2,835,021 fish in southern California, while 200,925 CPFV anglers landed 1,240, 100 fish in central and northern California.

Fishery dynamics of the California market squid (Loligo opalescens), as measured by satellite remote sensing

Novel data on the spatial and temporal distribution of fishing effort and population abundance are presented for the market squid fishery (Loligo opalescens) in the Southern California Bight, 1992−2000. Fishing effort was measured by the detection of boat lights by the Defense Meteorological Satellite Program (DMSP) Operational Linescan System (OLS). Visual confirmation of fishing vessels by nocturnal aerial surveys indicated that lights detected by satellites are reliable indicators of fishing effort. Overall, fishing activity was concentrated off the following Channel Islands: Santa Rosa, Santa Cruz, Anacapa, and Santa Catalina. Fishing activity occurred at depths of 100 m or less. Landings, effort, and squid abundance (measured as landings per unit of effort, LPUE) markedly declined during the 1997−98 El Niño; landings and LPUE increased afterwards. Within a fishing season, the location of fishing activity shifted from the northern shores of Santa Rosa and Santa Cruz Islands in October, the typical starting date for squid fishing in the Bight, to the southern shores by March, the typical end of the squid season. Light detection by satellites offers a source of fine-scale spatial and temporal data on fishing effort for the market squid fishery off California, and these data can be integrated with environmental data and fishing logbook data in the development of a management plan.

Current water supply conditions in California

This paper contains a brief report on the status of the California water supply situation on March 1, 1989, including a review of the antecedent conditions of the past two dry water years.

Geochemical evidence for enhanced upwelling and organic productivity during the late Quaternary on the continental margin of northern California

EXTRACT (SEE PDF FOR FULL ABSTRACT): Laminated sediments are preserved in upper Pleistocene sections of cores collected on the continental slope at water depths within the present oxygen-minimum zone from at least as far north as the Klamath River and as far south as Point Sur. Comparison of sediment components in the laminae with those delivered to sediment traps as pelagic marine "snow" show the dark/light lamination couplets are indeed annual (varves). ... The presence of carbon-, sulfur-, and metal-rich sediments, as well as lack of bioturbation, all support the theory that the oxygen-minimum zone in the northeastern Pacific Ocean was more intense - in fact, anoxic - during the late Pleistocene in response to greater coastal upwelling and higher organic productivity.

Integrating varve and tree-ring time series for southern California climate reconstruction: a 20th century outlook [abstract]

EXTRACT (SEE PDF FOR FULL ABSTRACT): Our objective is to combine terrestrial and oceanic records for reconstructing West Coast climate. Tree rings and marine laminated sediments provide high-resolution, accurately dated proxy data on the variability of climate and on the productivity of the ocean and have been used to reconstruct precipitation, temperature, sea level pressure, primary productivity, and other large-scale parameters. We present here the latest Santa Barbara basin varve chronology for the twentieth century as well as a newly developed tree-ring chronology for Torrey pine.

The top ten California floods of the 20th century

The purpose of this paper is to summarize the biggest northern California floods of the 20th century. Flooding in California can occur from different causes. At least three types of floods occur: 1. Winter general floods, which cover a large area. 2. Spring and early summer snowmelt floods unique to the higher-elevation central and southern Sierra Nevada, which occur about once in 10 years on the average. 3. Local floods from strong thunderstorms, with intense rain over a relatively small area. These originate in moist tropical or subtropical air and include the flash floods of the desert and other areas of southern California when remnants of eastern Pacific hurricanes get carried into the state.

Disease problems in shrimp sector in Khulna district of Bangladesh: a question of sustainability

Disease is the main restraining factor for the development of shrimp sector in Bangladesh. Both brackish water shrimp bagda (Penaeus monodon) and freshwater prawn golda, (Macrobrachium rosenbergii) farming in Bangladesh have been facing disease problem. A study on disease outbreak in both brackish water and freshwater small-scale shrimp farms (gher) in Khulna district was carried out through interviewing randomly selected 3-5% of shrimp farmers with a structured questionnaire during March to December, 2002. The study showed that 97% bagda farming ghers and 80% golda farming ghers were affected by disease. White spot disease was the severe disease for bagda, whereas, antenna rot was the main disease for freshwater prawn. Change of water and liming were carried out as control measures of disease for bagda shrimp farming, while it was only liming for golda farming. A small number of shrimp farmers (15%) used chemicals for treatment of shrimp diseases. Development of suitable farming technology to prevent disease contamination and innovation of proper treatments for diseases are required to overcome the disease problems for sustainable shrimp farming in Bangladesh.

The church's mission to the mountaineers of the South / by Archdeacon Neve, of Virginia, Archdeacon Spurr, of West Virginia, Archdeacon Wentworth, diocese of Lexington, Reverend S.C. Hughson, O.H.C., of Sewanee, Tenn., Reverend E.N. Joyner, diocese of Asheville, and Reverend W.S. Claiborne ; compiled by the Rev. Walter Hughson of the district of Asheville.

http://purl.oclc.org/KUK/KDL/B92-151-29579531

Study of the water consuption of the international tourism sector in the costal zone of southwest Europe

Dissertação de Mestrado, Gestão da Água e da Costa, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2009

The Ratios of Carbon, Nitrogen, and Phosphorus in a Wetland Coastal Ecosystem of Southern India

The fertility of the coastal and estuarine waters is of great concern because of its influence on the productivity of these waters. Seasonal variations in the distribution of organic carbon, total nitrogen and total phosphorus in the sediments of Kuttanad Waters, a part of the tropical Cochin Estuary on the south west coast of India, are examined to identify the contribution of sediments to the fertility of the aquatic systems. The adjoining region has considerable agricultural activity. The fresh water zones had higher quantities of silt and clay whereas the estuarine zone was more sandy. Organic carbon, total phosphorus and total nitrogen were higher in the fresh water zones and lower in the estuarine zones. Total phosphorus and organic carbon showed the lowest values during monsoon periods. No significant trends were observed in the seasonal distributions of total nitrogen. Ratios of C/N, C/P and N/P, and the phosphorus and nitrogen content indicate significant modification in the character of the organic matter. Substantial amounts of the organic matter can contribute to reducing conditions and modify diagenetic processes

An evaluation of the simulated water balance of Eurasia and northern Africa at 6000 yr B.P. using lake status data

Changes in the water balance of Eurasia and northern Africa in response to insolation forcing at 6000 y BP simulated by five atmospheric general circulation models have been compared with observations of changes in lake status. All of the simulations show enhancement of the Asian summer monsoon and of the high pressure cells over the Pacific and Central Asia and the Middle East, causing wetter conditions in northern India and southern China and drier conditions along the Chinese coast and west of the monsoon core. All of the models show enhancement of the African monsoon, causing wetter conditions in the zone between ca 10–20 °N. Four of the models show conditions wetter than present in southern Europe and drier than present in northern Europe. Three of the models show conditions similar to present in the mid-latitude continental interior, while the remaining models show conditions somewhat drier than present. The extent and location of each of the simulated changes varies between the models, as does the mechanism producing these changes. The lake data confirm some features of the simulations, but indicate discrepancies between observed and simulated climates. For example, the data show: (1) conditions wetter than present in central Asia, from India to northern China and Mongolia, indicating that the simulated Asian monsoon expansion is too small; (2) conditions wetter than present between ca. 10–30 °N in Africa, indicating that the simulated African monsoon expansion is too small; (3) that northern Europe was drier, but the area of significantly drier conditions was more localized (around the Baltic) than shown in the simulations; (4) that southern Europe was wetter than present, apparently consistent with the simulations, but pollen data suggest that this reflects an increase in summer rainfall whereas the models show winter precipitation, and (5) that the mid-latitude continental interior was generally wetter than present.