[1] Photomineralization of terrigenous dissolved organic matter (tDOM) in the Arctic Ocean is limited by persistent sea ice cover that reduces the amount of ultraviolet (UV) radiation reaching the underlying water column. UV-dependent processes are likely to accelerate as a result of shrinking sea ice extent and decreasing ice thickness caused by climatic warming over this region. In this study, we made the first quantitative estimates of photomineralization of tDOM in a coastal Arctic ecosystem under current and future sea ice regimes. We used an optical-photochemical coupled model incorporating water column optics and experimental measurements of photoproduction of dissolved inorganic carbon (DIC), the main carbon product of DOM photochemistry. Apparent quantum yields of DIC photoproduction were determined on water samples from the Mackenzie River estuary, the Mackenzie Shelf, and Amundsen Gulf. UV irradiances just below the sea surface were estimated by combining satellite backscattered and passive microwave radiance measurements with a radiative transfer model. The mean annual DIC photoproduction between 1979 and 2003 was estimated as 66.5 ± 18.5 Gg carbon in the surface waters of the southeastern Beaufort Sea, where UV absorption is dominated by chromophoric dissolved organic matter discharged by the Mackenzie River. This value is equivalent to 10% of bacterial respiration rates, 8% of new primary production rates and 2.8 ± 0.6% of the 1.3 Tg of dissolved organic carbon (DOC) discharged annually by the Mackenzie River into the area. During periods of reduced ice cover such as 1998, the latter value could rise to 5.1% of the annual riverine DOC discharge. Under an ice-free scenario, the model predicted that 150.5 Gg of DIC would be photochemically produced, mineralizing 6.2% of the DOC input from the Mackenzie River. These results show that the predicted trend of ongoing contraction of sea ice cover will greatly accelerate the photomineralization of tDOM in Arctic surface waters.

Photodecarboxylation (often stoichiometrically expressed as RCOOH + (1/2)O2 --> ROH + CO2) has long been postulated to be principally responsible for generating CO2 from photooxidation of dissolved organic matter (DOM). In this study, the quantitative relationships were investigated among O2 consumption, CO2 production, and variation of carboxyl content resulting from photooxidation of DOM in natural water samples obtained from the freshwater reaches of the Satilla River and Altamaha River in the southeastern United States. In terms of loss of dissolved organic carbon (DOC), loss of optical absorbance, and production of CO2, the rate of photooxidation of DOM was increased in the presence of Fe redox chemistry and with increasing O2 content. The ratio of photochemical O2 consumption to CO2 photoproduction ranged from approximately 0.8 to 2.5, depending on the O2 content, the extent of involvement of Fe, and probably the initial oxidation state of DOM as well. The absolute concentration of carboxyl groups ([-COOH]) on DOM only slightly decreased or increased over the course of irradiation, possibly depending on the stages of photooxidation, while the DOC-normalized carboxyl content substantially increased in the presence of Fe redox chemistry and sufficient O2. Both the initial [-COOH] and the apparent loss of this quantity over the course of irradiation was too small to account for the much larger production of CO2, suggesting that carboxyl groups were photochemically regenerated or that the major production pathway for CO2 did not involve photodecarboxylation. The results from this study can be chemically rationalized by a reaction scheme of (a) photodecarboxylation/ regeneration of carboxyl: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m-b(COOH)b or of (b) nondecarboxylation photooxidation: CxHyOz(COOH)m + aO2 + (metals, hv) --> bCO2 + cH2O2 + Cx-bHy'Oz'(COOH)m.

This study examined the effects of water temperature and the origin (terrestrial vs marine) and light history of chromophoric dissolved organic matter (CDOM) on the apparent quantum yields of carbon monoxide (CO) photoproduction for water samples collected along a salinity gradient (salinity range: 0-33) in the St. Lawrence estuarine system (Canada). The solar insolation-weighted mean apparent quantum yield of CO (phico) decreased as much as fourfold with increasing salinity and showed a strong positive correlation with the dissolved organic carbon-specific absorption coefficient at 254 nm. This suggests that terrestrial CDOM is more efficient at photochemically producing CO than is marine algae-derived CDOM and that aromatic moieties are likely involved in this photoprocess. CDOM photobleaching, mainly at the very early stage, dramatically decreased phico (by up to 6.4 times) for low-salinity samples, but photobleaching had little effect on the most marine sample. For a 20 degree C increase in temperature, phico increased by approximately 70% for low-salinity samples and 30-40% for saline samples. This study demonstrates that water temperature, as well as the CDOM's origin and light history, strongly affect the efficiency of CO photoproduction. These factors should be taken into account in modeling the photochemical fluxes of CO and other related CDOM photoproducts on varying spatiotemporal scales.

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We investigated the distribution, photoproduction, microbial uptake, and air-sea exchange of carbon monoxide (CO), a key photoproduct of chromophoric dissolved organic matter ( . Microbial CO uptake followed first-order kinetics in autumn while Hill-type, saturation, and inhibition kinetics were common in surface waters in spring. Bio-oxidation was the dominant CO loss term in autumn while gas exchange was almost equally important in spring. Higher photoproduction and slower bio-uptake in spring resulted in the wide autumn-spring differences in the [CO] distribution pattern and air-sea CO flux. CO cycling in cold northern waters differs both quantitatively and qualitatively from that in warmer seas.

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Early to Middle Ordovician strata, including Wenquan quartzite, occur widely in the Himalaya, Lhasa, and south Qiangtang blocks. The Wenquan quartzite occurs on the south side of the Lungmuco-Shuanghu Suture in the Qiangtang area, Tibet. A total of 145 analyses on detrital zircons from the quartzite show five age ranges of 520-700, ca. 800, 900-1100, 1800-1900, and 2400-2500 Ma, with particularly distinct age peaks of 625 and 950 Ma. The reliable youngest detrital zircon age is 525 Ma, and the oldest, 3180 Ma. Detrital zircons show large variations in Hf isotope composition, with depleted mantle model ages t DM (Hf) ranging from 750 to 3786 Ma. Based on data obtained in this study and by others, the main conclusions are as follows: 1) Low-grade metamorphic sedimentary rocks are distributed extensively in the south of the Lungmuco-Shuanghu Suture and are Phanerozoic in age; 2) Pan-African and Grenville-Jinning tectono-thermal events were well developed in the source region of the Wenquan quartzite; 3) the source region shows crustal addition and recycling of different periods; 4) Wenquan quartzite was derived from the Gondwana metamorphic basement, suggesting that the Qiangtang block is a Gondwanan fragment. Gondwana, Tibetan Plateau, detrital zircon, SHRIMP dating, Hf isotope, Pan-African movement, Grenville-Jinning movementCitation: Dong C Y, Li C, Wan Y S, et al. Detrital zircon age model of Ordovician Wenquan quartzite south of Lungmuco-Shuanghu Suture in the Qiangtang area, Tibet: Constraint on tectonic affinity and source regions.Arising from the wide application of in situ U-Pb dating techniques such as by the SHRIMP ion microprobe, age distribution model studies of detrital zircons from (meta-) sedimentary rocks play more and more important roles in tracing the source region of detrital materials, understanding the evolution of ancient basement, determining the formation age of sedimentary rocks, and revealing the tectonic affinity of different blocks. The low-grade metamorphic Wenquan quartzite of the Early to Middle Ordovician age is the oldest geological body recently identified in the south side of the Lungmuco-Shuanghu Suture, central Tibetan Plateau. This paper reports U-Pb ages and Hf isotope compositions of detrital zircons of the quartzite in order to better understand the source characteristics and tectonic affinity of the Southern Qiangtang block.

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