Changes in dissolved organic matter (DOM) amount and composition along nested headwater stream locations during baseflow and stormflow

Amount and composition of dissolved organic matter (DOM) were evaluated for multiple, nested stream locations in a forested watershed to investigate the role of hydrologic flow paths, wetlands and drainage scale. Sampling was performed over a 4‐year period (2008–2011) for five locations with drainage areas of 0.62, 3.5, 4.5, 12 and 79 ha. Hydrologic flow paths were characterized using an end‐member mixing model. DOM composition was determined using a suite of spectrofluorometric indices and a site‐specific parallel factor analysis model. Dissolved organic carbon (DOC), humic‐like DOM and fluorescence index were most sensitive to changes with drainage scale, whereas dissolved organic nitrogen, specific UV absorbance, Sr and protein‐like DOM were least sensitive. DOM concentrations and humic‐like DOM constituents were highest during both baseflow and stormflow for a 3.5‐ha catchment with a wetland near the catchment outlet. Whereas storm‐event concentrations of DOC and humic DOM constituents declined, the mass exports of DOC increased with increasing catchment scale. A pronounced dilution in storm‐event DOC concentration was observed at peak stream discharge for the 12‐ha drainage location, which was not as apparent at the 79‐ha scale, suggesting key differences in supply and transport of DOM. Our observations indicate that hydrologic flow paths, especially during storms, and the location and extent of wetlands in the catchment are key determinants of DOM concentration and composition. This study furthers our understanding of changes in DOM with drainage scale and the controls on DOM in headwater, forested catchments. Copyright © 2014 John Wiley & Sons, Ltd.     

Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds

Although organic compounds typically constitute a substantial fraction of the fine particulate matter (PM) in the atmosphere, their molecular composition remains poorly characterized. This is largely because atmospheric particles contain a myriad of diverse organic compounds, not all of which extract in a single solvent or elute through a gas chromatograph; therefore, a substantial portion typically remains unanalyzed. Most often the chemical analysis is performed on a fraction that extracts in organic solvents such as benzene, ether or hexane; consequently, information on the molecular composition of the water-soluble fraction is particularly sparse and incomplete.This paper investigates theoretically the characteristics of the water-soluble fraction by splicing together various strands of information from the literature. We identify specific compounds that are likely to contribute to the water-soluble fraction by juxtaposing observations regarding the extraction characteristics and the molecular composition of atmospheric particulate organics with compound-specific solubility and condensibility for a wide variety of organics. The results show that water-soluble organics, which constitute a substantial fraction of the total organic mass, include C2 to C7 multifunctional compounds (e.g., diacids, polyols, amino acids). The importance of diacids is already recognized; our results provide an impetus for new experiments to establish the atmospheric concentrations and sources of polyols, amino acids and other oxygenated multifunctional compounds.     

固相萃取—高温裂解—气相色谱质谱法测定西台晶间卤水中溶解性有机质

采用3种固相萃取材料(C18、XAD-8/4和PPL)分离富集西台吉乃尔盐湖卤水中的溶解性有机物(DOM),通过总有机碳/总氮分析(TOC/TN)、紫外—可见光谱分析、元素分析、傅里叶变换红外光谱分析(FTIR)、高温裂解—气相色谱质谱联用仪(Py-GC/MS)等对富集的有机物进行表征和分析方法比较。结果表明,西台吉乃尔盐湖卤水中的溶解性有机物主要有多糖类,芳香类、含氮类有机物,烷烃烯烃类化合物。PPL,C18和XAD-8/4的回收率分别为40±2%,7±2%和16±1%,虽然C18和XAD-8/4回收率较低,但3种吸附剂都有各自的特点,C18较易吸附烷烃烯烃类有机物,XAD-8/4较易吸附芳香类有机物,PPL较易吸附含N类有机物和多糖类有机物。     

Spatio-temporal changes in totally and enzymatically hydrolyzable amino acids of superficial sediments from three contrasted areas

Spatio-temporal changes in totally and enzymatically hydrolyzable amino acids (THAA and EHHA) and EHAA/THAA ratios of superficial sediments were assessed during 1997-1999 in three areas (i.e., the Gulf of Lions, the Bay of Biscay, and Central Chile) differing in their primary productivity. In all three areas, and even off Central Chile where a strong El Niño event took place during 1997-1998, spatial changes were always much greater than temporal ones. The factors affecting the spatial distributions of amino acid concentrations differed among areas. In the Gulf of Lions, sediment granulometry was apparently the most important driving force of THAA, EHAA, and EHAA/THAA, and there was no marked difference between stations located on the open slope and those in submarine canyons. Conversely, in the Bay of Biscay, there were clear differences between the stations located off Cap-Breton, on the open slope, and those in the Cap-Ferret canyon; the latter two featuring lower EHAA and THAA but higher EHAA/THAA. This pattern is likely to result from the predominance of different sources of organic matter and especially from the importance of continental inputs to the Cap-Breton canyon. Off Central Chile, amino acid concentrations and ratios were both maximal around 100 m depth, probably reflecting the interaction between the primary productivity gradient and the presence of an oxygen minimum zone (OMZ) reducing the degradation of sedimentary organics. When comparing the average values collected in the three areas studied, THAA and EHAA were highest in Central Chile, intermediate in the Bay of Biscay and lowest in the Gulf of Lions. EHAA/THAA ratios were also highest in Central Chile but were lowest in the Bay of Biscay. Differences between the Gulf of Lions and the Bay of Biscay could have been affected by sampling design. In Central Chile, the use of labile organic carbon to total organic carbon (C-LOM/TOC) and EHAA/THAA as indices of organic matter lability led to very similar results. This was not the case in the Bay of Biscay. It is therefore argued that the use of C-LOM/TOC should be restricted to highly productive areas.     

A comparison of two techniques for the isolation of adsorbed dissolved organic material from seawater

¹³C solid-phase NMR and pyrolysis-chemical ionization mass spectrometry were used to characterize adsorbed organic material isolated on an XAD-2 macroreticular resin. Pyrolysis-chemical ionization mass spectrometry was used directly to fingerprint the organics sorbed to a titanium foil exposed in the same marine environment. The XAD-2 isolate was shown to be fractionated relative to the native material and contaminated with the isolation resin.     

Biomonitoring of heavy metals and trace organics using the intertidal mussel Perna viridis in Hong Kong coastal waters

This paper presents the results of a 6-year (1998–2003) survey of trace toxics in the intertidal mussel Perna viridis conducted by the Hong Kong Environmental Protection Department. Concentrations of heavy metals and trace organics were measured in the soft bodies of P. viridis collected from five sites in Hong Kong waters, i.e. Wu Kai Sha (Tolo Harbour), Ma Wan (Northwest), Tsim Sha Tsui (Victoria Harbour), Tai Tam (Hong Kong South) and Lamma Island (Southern Waters) in order to establish the spatial patterns of contaminants in mussels. Among the metals analysed, Cd showed a significant concentration gradient in Hong Kong waters. The levels of Cd in P. viridis were significantly higher at Ma Wan as compared to the other sites studied. Ma Wan also had relatively higher concentrations of Pb. Mn concentrations were particularly prominent at Wu Kai Sha. Significantly higher concentrations of Hg and Cu were recorded at Tai Tam and Tsim Sha Tsui. Tai Tam and Wu Kai Sha had higher levels of V; whereas higher Ni concentrations were recorded at Lamma Island and Tai Tam. No clear spatial patterns for Al, As, Cr, Fe and Zn were observed.

Higher concentrations of PAHs in P. viridis were observed around urban centres impacted by sewage discharges (e.g. Tsim Sha Tsui); whereas higher PCB levels were found not only in Tsim Sha Tsui but also in less urbanised areas such as Lamma Island and Tai Tam, suggesting that these may be due to non-sewage related inputs. The study also shows that Northwest and Southern waters are subject to a higher degree of DDT pollution compared with other sites. Of the 17 dioxin compounds analysed, positive data were mostly recorded for two compounds which are of low toxicity (i.e. OCDD and 1,2,3,4,6,7,8-HpCDD) whereas the most toxic congeners (i.e. 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD) were not detected in the 6 years of monitoring. In general, the levels of OCDD in P. viridis were found to be higher in Tai Tam and Lamma Island in Southern Waters of Hong Kong.

This study found that the levels of some highly toxic heavy metals (i.e. Cd, Hg and Pb) in the mussel P. viridis did not exceed the recommended limits for shellfish as food in Hong Kong (i.e. Cd: 2.0 ppm; Hg: 0.5 ppm; Pb: 6.0 ppm wet weight). The levels of As and Ni in P. viridis were also well below the action limits set by the US FDA (i.e. As: 86 ppm; Ni: 80 ppm wet weight). DDT and PCB contaminations in P. viridis were below the concentrations of concern. Compared with data obtained in the 1980s, the current levels of DDTs in P. viridis were 4–16 times lower; whereas Pb concentrations recorded in Tsim Sha Tsui have also been lowered significantly. This is mainly related to reduction in local and regional pollution sources in the past 20 years.     

Contribution of Secondary VOC to the Composition of Aqueous Atmospheric Particles: A Modeling Approach

Measurements show that 20–60% of the carbon mass present in fine atmospheric particulate matter consists of water soluble organic compounds (WSOC). However, only 5–20% of this WSOC has been identified, mainly as dicarboxylic acids. Because of their high solubility in water, multifunctional secondary compounds derived from the gas-phase oxidation of volatile organic compounds (VOC) are suspected to be key contributors to the WSOC. To test this assumption, an estimate of aqueous uptake of secondary VOC was included in a highly detailed gas-phase mechanism which treats explicitly the formation of the secondary VOC from a set of representative primary species. Simulations were conducted for 2 scenarios, representing typical rural and urban areas. It was observed that the uptake of secondary VOC can lead to WSOC mass concentrations in the range of a few C m^–3, in fairly good agreement with typical WSOC mass concentrations measured. Speciation of WSOC was found to be mainly as tri- or higher multifunctional hydroxy-carbonyl species and hydroxy-hydroperoxide-carbonyl species, in urban and rural environments, respectively. However, it was also found that taking into account only the absorption of secondary VOC does not bring the carboxylic acids mass concentration in agreement with measurements. An attempt was made to explain this discrepancy by introducing chemistry occurring within deliquescent aerosols.     

Field expansion and reallocation in the Sahel - land use pattern dynamics in a fluctuating biophysical and socio-economic environment

The paper addresses the dynamic relationship between the human use of land and alterations in the biophysical environment, demographic pressure or socio-economic conditions. An empirical study from the Sahelian zone in northern Burkina Faso illustrates the dynamics of cultivation pattern at the village level and the changing priorities given to different landscape units over time. Field measurements, aerial photos and satellite images from seven successive years provide information on land use pattern changes from 1945 to 1995. A household survey illustrates how socio-economic and cultural parameters enable and constrain land use strategies at the farm level.     

Biomonitoring of heavy metals and trace organics using the intertidal mussel Perna viridis in Hong Kong coastal waters

This paper presents the results of a 6-year (1998–2003) survey of trace toxics in the intertidal mussel Perna viridis conducted by the Hong Kong Environmental Protection Department. Concentrations of heavy metals and trace organics were measured in the soft bodies of P. viridis collected from five sites in Hong Kong waters, i.e. Wu Kai Sha (Tolo Harbour), Ma Wan (Northwest), Tsim Sha Tsui (Victoria Harbour), Tai Tam (Hong Kong South) and Lamma Island (Southern Waters) in order to establish the spatial patterns of contaminants in mussels. Among the metals analysed, Cd showed a significant concentration gradient in Hong Kong waters. The levels of Cd in P. viridis were significantly higher at Ma Wan as compared to the other sites studied. Ma Wan also had relatively higher concentrations of Pb. Mn concentrations were particularly prominent at Wu Kai Sha. Significantly higher concentrations of Hg and Cu were recorded at Tai Tam and Tsim Sha Tsui. Tai Tam and Wu Kai Sha had higher levels of V; whereas higher Ni concentrations were recorded at Lamma Island and Tai Tam. No clear spatial patterns for Al, As, Cr, Fe and Zn were observed.Higher concentrations of PAHs in P. viridis were observed around urban centres impacted by sewage discharges (e.g. Tsim Sha Tsui); whereas higher PCB levels were found not only in Tsim Sha Tsui but also in less urbanised areas such as Lamma Island and Tai Tam, suggesting that these may be due to non-sewage related inputs. The study also shows that Northwest and Southern waters are subject to a higher degree of DDT pollution compared with other sites. Of the 17 dioxin compounds analysed, positive data were mostly recorded for two compounds which are of low toxicity (i.e. OCDD and 1,2,3,4,6,7,8-HpCDD) whereas the most toxic congeners (i.e. 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD) were not detected in the 6 years of monitoring. In general, the levels of OCDD in P. viridis were found to be higher in Tai Tam and Lamma Island in Southern Waters of Hong Kong.This study found that the levels of some highly toxic heavy metals (i.e. Cd, Hg and Pb) in the mussel P. viridis did not exceed the recommended limits for shellfish as food in Hong Kong (i.e. Cd: 2.0 ppm; Hg: 0.5 ppm; Pb: 6.0 ppm wet weight). The levels of As and Ni in P. viridis were also well below the action limits set by the US FDA (i.e. As: 86 ppm; Ni: 80 ppm wet weight). DDT and PCB contaminations in P. viridis were below the concentrations of concern. Compared with data obtained in the 1980s, the current levels of DDTs in P. viridis were 4–16 times lower; whereas Pb concentrations recorded in Tsim Sha Tsui have also been lowered significantly. This is mainly related to reduction in local and regional pollution sources in the past 20 years.     

Determination of dissolved organic matter in streamwater using visible spectrophotometry: A reply

A reply to Finlayson (1986) suggesting that the priority should be for more widespread measurement of dissolved organic matter, without the need for special equipment. The use of chemical oxygen demand is also clarified.