Determination of Partition Coefficients for Selected PAHs between Water and Dissolved Organic Matter

The fate and transport of highly hydrophobic chemicals are affected by the partitioning between water and dissolved organic carbon. Large variation in the partition coefficient (K_DOCw) is often found, due to the selection of model organic matter or potential experimental artifacts. To investigate the roles of the type of organic matter on the partitioning of highly hydrophobic compounds, the partition coefficients of eight selected polycyclic aromatic hydrocarbons (PAHs), with 3–6 aromatic rings, were determined using a passive dosing/extraction method between water and model dissolved organic matter (humic acid, fulvic acid, sodium dodecyl sulfate micelle (SDS), and 2‐hydroxypropyl‐β‐cyclodextrin). Although the K_DOCw values for 3–4 ring PAHs in this study were close to those reported in the literature, experimental K_DOCw values between Aldrich humic acid (AHA) and water were higher than values reported in the literature for 5–6 ring PAHs. The K_DOCw values were highest for AHA, followed by SDS and Suwannee river fulvic acid (SFA). The slopes of the linear regression between log K_DOCw and log K_ow were 1.23 (± 0.13), 0.82 (± 0.09), and 0.59 (± 0.13) for AHA, SDS, and SFA, respectively. The differences in the K_DOCw values between AHA and the other organic matter (SDS, SFA, and CD) increased with increasing hydrophobicity of the PAHs, showing that the sorption of highly hydrophobic chemicals to the humic acid fraction may be important in the presence of mixed organic matter.     

太湖典型植物氨基酸组成特征及其对水环境的影响

在太湖两个不同湖区(东太湖和贡湖)各选择了8种不同类型的典型水生植物和1种陆生植物全株作为研究对象,采用邻苯二甲醛柱前衍生-反相高效液相色谱法对其中15种氨基酸的组成特征进行了分析,并探讨了植物来源氨基酸对湖泊水环境的影响.结果表明东太湖区域植物体中总可水解氨基酸(THAAs)的平均含量为861.6±182.96μmol/g,贡湖区域植物体中THAAs平均含量为700.0±232.3μmol/g;不同类型植物体中THAAs的含量大小依次为:沉水植物、浮叶植物挺水植物陆生植物;其中天冬氨酸、谷氨酸、精氨酸、丙氨酸和赖氨酸是THAAs的主要组成部分,这5种氨基酸的摩尔浓度占氨基酸总量的50%以上;太湖植物中THAAs所含的氮元素对植物总氮的贡献在30.7%~94.7%之间,是植物体氮元素的主要组分,也是内源氮输入的主要来源.东太湖区域采集的植物样品中各氨基酸的浓度比例与东太湖水体氨基酸组成差异较大,但与沉积物氨基酸组成较吻合,表明东太湖植物来源的有机质和氨基酸是沉积物中有机质和氨基酸的重要来源.     

Mercury concentrations and omega-3 fatty acids in fish and shrimp: Preferential consumption for maximum health benefits

The consumption of fish and shrimp containing omega-3 fatty acids can result in protective health effects including a reduced risk of cardiovascular disease, stroke, and diabetes. These protective effects may be decreased by the presence of mercury in the muscle tissue of fish and shellfish. Mercury can increase the risk of cardiovascular problems and impede neurological development. The objective of this project was to determine appropriate consumption amounts of selected fish species and shrimp based on mercury levels and recommended intake levels of omega-3 fatty acids. Species that are high in omega-3s and low in mercury include salmon, trout, and shrimp. Species with both high levels of mercury and omega-3 fatty acids include tuna, shark, and halibut, swordfish, and sea bass.     

铜绿微囊藻中的紫外保护物质类菌孢素氨基酸(MAAs)与水华形成机制探讨

类菌孢素氨基酸(mycosporine-like amino acids, 间称MAAs)存在于许多生物体内,对紫外辐射(UVR)有较高的吸收能力,被认为有保护细胞、减少UVR损伤的功能. 通过对从太湖分离、室内培养的铜绿微囊藻和以微囊藻为优势种类的太湖浮游植物样品的吸收光谱和反相高效液相色谱分析,发现铜绿微囊藻和太湖浮游植物都含有shinorine和porphyra-334两种MAAs,但以shinorine为主. 本文还讨论了MAAs与铜绿微囊藻水华形成的关系.     

The dynamic balance between organic acids and circumneutral groundwater in a large boreal peat basin

Large raised bogs and patterned fens cover 56% of the landscape in the Glacial Lake Agassiz region of northern Minnesota (USA). Organic acids supply most of the acidity in the surface water of the bogs, but groundwater upwelling from the underlying glacial deposits neutralizes these organic acids within deep peat. Substantial concentrations of organic acids also occur in the surface waters of fens mixed with variable amounts of inorganic solutes contributed by groundwater discharge. We used a triprotic analog model to determine the extent to which organic acids in fen and bog waters behave as strong or weak acids. The modeling approach optimized charge balance by calibrating estimates of mole site density in the DOC (dissolved organic carbon) of surface and pore waters with estimates of triprotic acid dissociation constants. Before the calibration process, all of the bog waters and 76% of the fen waters had more than +20% imbalance in charge balance. After calibration, more than 75% of all waters were electrochemically balanced within 20%. In the best calibration, the mole site denisty of bog DOC was estimated as 0.05 mmol/mmol C., approximately six times smaller than that estimated for fen DOC or the DOC in the fen deeper fen peats that underlie all bog landforms. The three modeled de-protonation constants were; pK_a1=3.0, pK_a2=4.5 and pK_a3=7.0 for the bog DOC, and; pK_a1=5.2, pK_a2= 6.5 and pK_a3=7.0 for the fen DOC. Bog DOC, behaves as a strong acid despite its small mole site density. The DOC in bog runoff can therefore theoretically acidify the surface waters in adjacent fens wherever these waters do not receive sufficient buffering alkalinity from active groundwater seepage.     

热带富营养化湖泊中浮游植物的脂肪酸组成与分布

星湖位于广东省．是一个热带地区的湖泊．本文测定和分析了该湖的两个子湖仙女湖和中心湖浮游植物群落的脂肪酸组成,探讨了浮游植物群落特征与脂肪酸组成之间的关系．两个子湖的富营养化程度较高,其中中心湖更严重．仙女湖的浮游植物群落以蓝藻为主导,而在中心湖则蓝藻或金藻占优势．浮游植物样品中检测到的脂肪酸碳链长为16碳到22碳．其中饱和脂肪酸和单不饱和脂肪酸种类较少,均有3种;而高不饱和脂肪酸的种类相对较多．两个子湖的脂肪酸均以饱和脂肪酸为主,高不饱和脂肪酸浓度相对较低．对于单一的脂肪酸种类来说,C16：0浓度最高,其浓度与蓝藻数量有很高的相关性(R^2=0．955,P=0．001),表明样品中的C16：0主要来源于蓝藻．而富含EPA(二十碳五烯酸)的硅藻和隐藻生物量高时其浮游植物的EPA浓度也较高;在中心湖中高浓度的DHA(二十二碳六烯酸)主要来源于金藻总之．两个子湖泊的脂肪酸组成与浮游植物群落结构特征基本一致．     

马来眼子菜体内抑藻物质分离及常见脂肪酸抑藻效应

提取马来眼子菜植物体内的抑藻物质,分离得到一活性组分,气质联用(GC-MS)鉴定其主要为脂肪酸类物质,抑制羊角月牙藻的半效应浓度(EC50,3d)为7.90mg/L.测定组分中含有的8种脂肪酸与油酸单独及联合作用对羊角月牙藻的抑藻效果,结果证实脂肪酸类物质具有化感抑藻效应,其抑藻效果与其碳链长度及其不饱和度有关,碳链越短其抑藻活性越高,不饱和脂肪酸的抑藻效应大于同碳链饱和脂肪酸,多种脂肪酸联合作用时具有协同作用.分离过程中也得到另一甾醇组分,其对羊角月牙藻没有明显抑制作用,且对脂肪酸类物质的抑藻效果没有影响.     

Correlations between fatty acid composition of seston and zooplankton and effects of environmental parameters in a eutrophic Siberian reservoir

During two sampling seasons we analyzed on weekly basis fatty acid (FA) composition of seston fraction <130 μm and zooplankton fraction >130 μm, and compared them using a multivariate canonical correlation analysis (CCA). Besides, we evaluated a possible impact of water temperature and inorganic nutrients on FA composition of the seston and the zooplankton.In spite of significant differences in percentages of several individual FAs, we found very strong canonical correlation (cross-correlation, 1-week lag) between FA composition of the seston and the zooplankton. The most important factor, providing the overall canonical cross-correlation between FA profiles of the seston and the zooplankton fractions was eicosapentaenoic acid (20:5ω3, EPA). FA composition of the zooplankton fraction had comparatively poor correlations with taxonomic composition of the zooplankton. Thus, seasonal variations of FA composition of the zooplankton were determined primarily by seasonal changes in FA composition of the seston, rather than by taxonomic differences of FA profiles between rotifers, cyclopoids and cladocerans. FA composition of the seston was strongly affected by its taxonomic composition, namely by that of phytoplankton. According to CCA, the highest factor loadings pertained to diatoms interacting with their marker acids, including EPA, and cyanobacteria and greens, interacting with their marker acids. Ciliates and small rotifers composed considerable and sometimes major part of the seston biomass, but according to CCA their contributions to seasonal variations of the total FA profile of the seston were insignificant. This finding indirectly support the conclusion of the other authors, that the main source of FAs presented in ciliates and rotifers must be sought in algae and that they do not modify FA composition of food consumed, apart from repackaging it.Water temperature was the principal environmental parameter which drove the overall variations of FA composition. Factor loadings for the inorganic nutrients were comparatively negligible. The main contribution in the seasonal variation of FA composition of the seston was given by negative interaction between water temperature and percentage of EPA in the seston.     

Sea-floor fissures, biological communities and sediment fatty acids of the Northern Okushiri Ridge, Japan Sea: Implications for possible methane seepage

A biological community was discovered in the Northern Okushiri Ridge, northeastern Japan Sea. The community was closely associated with sea-floor fissures, and presumed to be supported by methanotrophic and/or thiotrophic bacterial production. Sediments inside of and in the vicinity of the fissures were collected, and the short-chain (C_9–20) sediment fatty acids were analyzed for amounts and compositions. The fatty acid compositions were compared with those from a known methane seep and a submarine volcano in the Sagami Bay, central Japan, and from a whale skeleton at the Torishima Seamount, northwestern Pacific Ocean. As a result, a close relationship between the sediments from the Northern Okushiri Ridge, the known methane-seep, and the whale skeleton was found. This finding represents the first discovery of methane seepage and associated biological communities in the Japan Sea. This also supports the hypothesis that the eastern margin of the northern Japan Sea is at the early stage of new subduction.     

Protein diagenesis in Patella shells: Implications for amino acid racemisation dating

The inter- and intra-crystalline fractions of Patella vulgata limpets recovered from archaeological sites in Northern Spain (covering Neolithic, Mesolithic, Magdalenian, Solutrean, and Aurignacian periods) were examined for amino acid composition and racemisation over time. The calcitic apex and rim areas of the shells were found to probably be composed of similar proteins, as the D/L values and amino acids were comparable and varied in the same way with increasing age; however, the mineral structures present in these areas differed. The aragonitic intermediate part of the shell showed a distinctly different amino acid composition and mineral structure. The main protein leaching from the inter-crystalline fraction occurred within the first 6000 yr after the death of the organism. In contrast, the intra-crystalline fraction — comprised of a different protein composition than the inter-crystalline fraction — appeared to behave as a closed system for at least 34 ka, as reflected by the lack of a significant decrease in the amino acid content; however, changes in the amino acid percentages occurred during this period. The concentration of aspartic acid remained almost constant with age both in inter- and intra-crystalline proteins, and its contribution to the total amino acid content increased with age at the expense of other amino acids such as glutamic acid, serine, glycine and alanine. Temperature is thought to play a key role in the amino acid racemisation of P. vulgata and could explain why in the localities belonging to the Gravettian and Solutrean period, which formed during relatively cold conditions, D/L values were similar to those detected in shells from sites formed during the Magdalenian.     

Compound-specific radiocarbon dating of Ross Sea sediments: A prospect for constructing chronologies in high-latitude oceanic sediments

We present an overview of the problems relating to the development of sedimentary chronologies for Antarctic margin sediments, and review the recent application of compound-specific radiocarbon dating methods for resolving them. Radiocarbon dating of solvent-extractable, short-chain (C₁₄, C₁₆, and C₁₈) fatty acids isolated from surface sediments of the Ross Sea, Antarctica, revealed their ages to be consistent with that of the modern dissolved inorganic carbon (DIC) reservoir age (pre-bomb, Δ¹⁴C≈−150‰; post-bomb, Δ¹⁴C≈−100‰) in this region. This contrasts sharply with the radiocarbon ages of bulk organic matter in the corresponding sediments are substantially older (Δ¹⁴C=−298‰ to −712‰). Furthermore, the radiocarbon ages of these fatty acids progressively increase with the core depth. These results clearly show a utility of the compound-specific radiocarbon dating for developing sediment chronologies in the Antarctic margin sediments. This approach is potentially applicable to Arctic Ocean, as well as other areas of Southern Ocean where similar interferences by fossil or pre-aged carbon inputs have hindered the progress in the development of late Quaternary paleoceanographic records.     

Diatom valve distribution and sedimentary fatty acid composition in Larsen Bay, Eastern Antarctica Peninsula

During austral summer 2006-2007, five sediment cores were recovered from the Eastern Antarctic Peninsula (EAP) continental shelf. Microscopic observations and sediment fatty acid (FA) composition analyses were carried out to investigate whether the drastic changes at the sea surface in EAP may be reflected in the sedimentary record. A sharp decrease in the number of diatom valves was observed below 2 cm depth. This difference between the upper 2 cm of sediment and the deeper part of the sediment column was attributed to the drastic change in the upper water column conditions after the collapse of the ice shelves, which allowed the arrival of phytoplankton debris and fresh organic matter to the sea floor in EAP. The presence of bacterial-, zooplankton- and detrital-related FA throughout EAP cores suggests that there has been an input of older and more refractory organic matter into the region, presumably by lateral transport before the Larsen ice shelves disintegration.     

Importance of environment on the order of mineral weathering in olivine basalts,Hawaii

Examination of weathering rinds from lava flows on Hawaii with backscatter electron microscopy and electron micro-probe analysis reveals that olivine weathers more slowly than adjacent clinopyroxene and plagioclase in environments with a paucity of organic acids. Yet when weathering rinds are in contact with abundant organic acids secreted by lichens, olivine weathers before clinopyroxene and plagioclase weathers last. The exception to Goldich's widely accepted mineral stability series in organic-poor environments runs counter to a thermodynamics explanation for the order of mineral weathering and illustrates the importance of the biogeochemical environment.     

Free Amino Acids Content in Some Halophytes under Salinity Stress in Arid Environment,Jordan

The variation in free amino acids concentration was examined in halophytes under salt stress conditions during spring and autumn in an arid environment, Jordan. The experiment was conducted in the southern region of the Jordan valley, using four different halophytes namely: Atriplex halimus, Atriplex nummularia, Tamarix aphylla L., and Portulaca oleracea L. Free amino acid concentrations showed changeable patterns under salinity stress conditions compared to the non‐stress (control) with respect to plant species and seasonal variation. In general, the amino acid pool during the spring experienced increases in A. halimus with increasing salinity; and decreased in A. nummularia, P. oleracea L., and T. aphylla L., respectively. Whereas, during the autumn, the overall amino acids decreased in A. halimus and A. nummularia, and increased in T. aphylla L. and P. oleracea with increasing salinity. The amino acid pool concentrations of A. halimus L. during the autumn was similar to that in spring under stress condition. Similarly, T. aphylla L. and P. oleracea showed higher rates in the autumn. In contrast, A. nummularia L. exhibited a slight increase in amino acid composition in the autumn under stress conditions. The plantation of salt tolerant plants such as halophytes in saline sodic soils showed an effective decline in soil salinity and can be recommended to be used as a bioreclamation method instead of the traditional leaching method, which requires large amount of fresh water.     

Particulate matter fluxes in the southern and central Kara Sea compared to sediments: Bulk fluxes, amino acids, stable carbon and nitrogen isotopes, sterols and fatty acids

The Kara Sea is one of the arctic marginal seas strongly influenced by fresh water and river suspension. The highly seasonal discharge by the two major rivers Yenisei and Ob induces seasonal changes in hydrography, sea surface temperature, ice cover, primary production and sedimentation. In order to obtain a seasonal pattern of sedimentation in the Kara Sea, sediment traps were deployed near the river mouth of the Yenisei (Yen) as well as in the central Kara Sea (Kara) within the framework of the German–Russian project “Siberian River run-off; SIRRO”. Two and a half years of time-series flux data were obtained between September 2000 and April 2003 and were analyzed for bulk components, amino acids, stable carbon and nitrogen isotopes as well as sterols and fatty acids.Sediment trap data show that much of the annual deposition occurred under ice cover, possibly enhanced by zooplanktonic activity and sediment resuspension. An early bloom of ice-associated algae in April/May occurred in the polynya area and may have been very important to sustain the life cycles of higher organisms after the light limitation of the winter months due to no/low insolation and ice cover. The strong river input dominated the months June–August in the southern part of the Kara Sea. The central Kara Sea had a much shorter productive period starting in August and was less affected by the river plumes. Despite different time-scales of sampling and trapping biases, total annual fluxes from traps were in the same order of magnitude as accumulation rates in surface sediments. Terrestrial organic carbon accumulation decreased from 10.7 to 0.3 g C m⁻² a⁻¹ from the riverine source to the central Kara Sea. Parallel to this, preservation of marine organic matter decreased from 10% to 2% of primary productivity which was probably related to decreasing rates of sedimentation.     

Simultaneous analyses and applications of multiple fluorobenzoate and halide tracers in hydrologic studies

An analytical method that employs ion chromatography has been developed to exploit the use of fluorobenzoic acids (FBAs) and halides more fully as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g. nitrate and sulphate). The usefulness of this analytical method is demonstrated in both field and laboratory tracer experiments. The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the USA—mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need—reveal several insights about tracer transport behaviour: (1) bromide and FBAs are not always transported conservatively; (2) the delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy; (3) use of iodine as a hydrologic tracer should take into account the different sorption behaviours of iodide and iodate and the possible conversion of iodine's initial chemical form; (4) the transport behaviour of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large‐scale field tracer experiments. Copyright © 2005 John Wiley & Sons, Ltd.     

The feasibility of isolation and detection of fullerenes and carbon nanotubes using the benzene polycarboxylic acid method

The incorporation of fullerenes and carbon nanotubes into electronic, optical and consumer products will inevitably lead to the presence of these anthropogenic compounds in the environment. To date, there have been few studies isolating these materials from environmental matrices. Here we report a method commonly used to quantify black carbon (BC) in soils, the benzene polycarboxylic acid (BPCA) method, for measurement of two types of single walled carbon nanotubes (SWCNTs), two types of fullerenes and two forms of soot. The distribution of BC products (BPCAs) from the high pressure and high temperature oxidation illustrates the condensed nature of these compounds because they form predominantly fully substituted mellitic acid (B6CA). The conversion of carbon nanoparticles to BPCAs was highest for fullerenes (average of 23.2 ± 4.0% C recovered for both C₆₀ and C₇₀) and lowest for non-functionalized SWCNTs (0.5 ± 0.1% C). The recovery of SWCNTs was 10 times higher when processed through a cation-exchange column, indicating the presence of metals in SWCNTs compromises the oxidation chemistry. While mixtures of SWCNTs, soot and sediment revealed small losses of black carbon during sample processing, the method is suitable for quantifying total BC. The BPCA distribution of mixtures did not agree with theoretical mixtures using model polyaromatic hydrocarbons, suggesting the presence of a matrix effect. Future work is required to quantify different types of black carbon within the same sample.