Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin.Part II: Substituted Phenols in Berlin Surface Water

In a surface water screening, 30 representative surface water samples collected from rivers, canals, and lakes in Berlin were investigated for the presence of 22 substituted phenols. The phenols selected include the 11 phenols considered as “priority pollutants” by the US Environmental Protection Agency (US-EPA). Surface water samples were extracted applying solid-phase extraction with styrenedivinylbenzene adsorbent. The recoveries, determined in spiking experiments, were between 80 % and 103 %. After derivatization with N-(tert-butyldimethylsilyl)-N-methyl-trifluoroacetamide (MTBSTFA) the samples were analyzed by capillary gas chromatography-mass spectrometry (GC-MS). Phenol, cresols, 2-ethylphenol, 2-chlorophenol, 4-chloro-3-methylphenol, pentachlorophenol, 2-nitrophenol, and 4-nitrophenol were detected in the surface water samples at concentrations between 0.02 μg/L and 7.8 μg/L, respectively. The distribution of these residues in the Berlin surface waters showed that the phenolic residues, with the exception of pentachlorophenol and 2-ethylphenol, do not originate primarily from municipal sewage treatment plants discharges. Some of the phenols are formed naturally or occur as ubiquitous anthropogenic contaminants in the aquatic system.     

Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Long-range weather forecasts through numerical and empirical methods

There has been much improvement in numerical weather prediction since L.F. Richardson (1922, Weather Prediction by Numerical Process, Cambridge University Press, Cambridge, p. 236) wrote his famous book. NWP has primarily been successful in improving day-by-day forecasts starting from an observed detailed Initial Condition (IC) out to about a week. The purpose of this paper is to discuss first the state of the art in long-range NWP by presenting results of a new large numerical experiment (named DERF90; from Dynamical Extended Range Forecasting in 1990 out to 90 days) conducted at the National Meteorological Center (NMC) during the summer and autumn of 1990 (Section 2). One hundred and twenty eight 90-day global forecasts were made from successive daily initial conditions (IC), thus giving us ample opportunity to assess skill of forecasts at lead times beyond 1 week.We then move on to define the notion of a limit of predictability (LOP), and following a procedure by Lorenz (1982), give a numerical estimate of the LOP using the DERF90 data set. We then produce a list of reasons, as to why this estimate (LOP = 18 days) should not be taken too literally. In particular, we argue that the LOP varies as a function of the flow itself, and it would be (much) larger if we had, as we will ultimately, a coupled ocean-atmosphere model for making long-lead forecasts. Last, but not least, we present results of empirical forecasts that point to modest but significant skill well beyond the traditional LOP (a few weeks).A specific recent example of empirical forecasting is discussed. Through Canonical Correlation Analysis (CCA), experimental forecasts are being made for the United States surface temperatures at lead times of several seasons. While modest, the skill is significant in that it defies the existence or a 3-week LOP, and so demonstrates the potential for model improvements.     

中国超级杂交稻在孟印缅地区的生产潜力模拟

水稻是孟加拉国、印度和缅甸最重要的粮食作物,研究中国超级杂交稻对孟印缅地区的水稻增产潜力,对于保障孟中印缅经济走廊的粮食安全与区域可持续发展具有重要的现实意义。在全面收集孟印缅地区气候、土壤、田间管理信息和农业统计数据的基础上,结合中国籼型杂交稻F优498和丰两优4号的品种信息和区试数据,通过EPIC模型模拟了1996-2005年雨季孟印缅3国在不同情景下的超级稻生产潜力,并分析了孟印缅地区主要胁迫因子对超级稻单产潜力的影响。研究表明：① 中国超级杂交稻在孟印缅地区2000年的灌溉和施肥水平下单产潜力为10.22 t/ha,在充分灌溉且合理施肥的水平下单产潜力为11.33 t/ha。② 孟印缅地区雨季稻的增产空间达22771万t,水稻增产潜力最大的地区是印度的恒河平原东部、印度半岛东南沿海与缅甸的伊洛瓦底三角洲。③ 印度德干高原东北部、西南部和印度大平原西北部需要进一步完善灌溉设备以满足高产水稻用水,缅甸的中南部平原地区和印度的东北地区则需要增施氮肥以满足高产水稻用肥。     

Imbalance in the carbonate budget of surficial sediments in the North Atlantic Ocean: variations over the last millenium?

Fluxes contributing to the particulate carbonate system in deep-sea sediments were investigated at the BENGAL site in the Porcupine Abyssal Plain (Northeast Atlantic). Deposition fluxes were estimated using sediment traps at a nominal depth of 3000 m and amounted to 0.37±0.1 mmol C m⁻² d⁻¹. Dissolution of carbonate was determined using flux of total alkalinity from in situ benthic chambers, is 0.4±0.1 mmol C m⁻² d⁻¹. Burial of carbonate was calculated from data on the carbonate content of the sediment and sedimentation rates from a model age based on ¹⁴C dating on foraminifera (0.66±0.1 mmol C m⁻² d⁻¹). Burial plus dissolution was three times larger than particle deposition flux which indicates that steady-state is not achieved in these sediments. Mass balances for other components (BSi, ²¹⁰Pb), and calculations of the focusing factor using ²³⁰Th, show that lateral inputs play only a minor role in this imbalance. Decadal variations of annual particle fluxes are also within the uncertainty of our average. Long-term change in dissolution may contribute to the imbalance, but can not be the main reason because burial alone is greater than the input flux. The observed imbalance is thus the consequence of a large change of carbonate input flux which has occured in the recent past. A box model is used to check the response time of the solid carbonate system in these sediments and the time to reach a new steady-state is in the order of 3 kyr. Thus it is likely that the system has been perturbed recently and that large dissolution and burial rates reflect the previously larger particulate carbonate deposition rates. We estimate that particulate carbonate fluxes have certainly decreased by a factor of at least 3 and that this change has occurred during the last few centuries.     

Comparison of the LEW88516 and ALHA77005 martian meteorites: Similar but distinct

Abstract By mineral and bulk compositions, the Lewis Cliff (LEW) 88516 meteorite is quite similar to the ALHA77005 martian meteorite. These two meteorites are not paired because their mineral compositions are distinct, they were found 500 km apart in ice fields with different sources for meteorites, and their terrestrial residence ages are different. Minerals in LEW88516 include: olivine, pyroxenes (low- and high-Ca), and maskelynite (after plagioclase); and the minor minerals chromite, whitlockite, ilmenite, and pyrrhotite. Mineral grains in LEW88516 range up to a few mm. Texturally, the meteorite is complex, with regions of olivine and chromite poikilitically enclosed in pyroxene, regions of interstitial basaltic texture, and glass-rich (shock) veinlets. Olivine compositions range from Fo₆₄ to Fo₇₀, (avg. Fo₆₇), more ferroan and with more variation than in ALHA77005 (Fo₆₉ to Fo₇₃). Pyroxene compositions fall between En₇₇Wo₄ and En₆₅Wo₁₅ and in clusters near En₆₃Wo₉ and En₅₃Wo₃₃, on average more magnesian and with more variation than in ALHA77005. Shock features in LEW88516 range from weak deformation through complete melting. Bulk chemical analyses by modal recombination of electron microprobe analyses, instrumental neutron activation, and radiochemical neutron activation confirm that LEW88516 is more closely related to ALHA77005 than to other known martian meteorites. Key element abundance ratios are typical of martian meteorites, as is its non-chondritic rare earth pattern. Differences between the chemical compositions of LEW88516 and ALHA77005 are consistent with slight differences in the proportions of their constituent minerals and not from fundamental petrogenetic differences. Noble gas abundances in LEW88516, like those in ALHA77005, show modest excesses of ⁴⁰Ar and ¹²⁹Xe from trapped (shock-implanted) gas. As with other ALHA77005 and the shergottite martian meteorites (except EETA79001), noble gas isotope abundances in LEW88516 are consistent with exposure to cosmic rays for 2.5–3 Ma. The absence of substantial effects of shielding from cosmic rays suggest LEW88516 spent this time as an object no larger than a few cm in diameter.     

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ¹⁸O and δ³⁴S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O₂ as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)_aq as an oxidant with varying δ¹⁸O_H2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ³⁴S_SO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O₂) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O₂ varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (ε¹⁸O_SO4-H2O) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured value was then used to estimate the oxygen isotope fractionation effects between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ¹⁸O_SO4 values in the biological and abiotic experiments, it is suggested that δ¹⁸O_SO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)_aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions.     

Estimation of groundwater evaporation and salt flux from Owens Lake, California, USA

Groundwater evaporation and subsequent precipitation of soluble salts at Owens Lake in eastern California have created one of the single largest sources of airborne dust in the USA, yet the evaporation and salt flux have not been fully quantified. In this study, we compare eddy correlation, microlysimeters and solute profiling methods to determine their validity and sensitivity in playa environments. These techniques are often used to estimate evaporative losses, yet have not been critically compared at one field site to judge their relative effectiveness and accuracy. Results suggest that eddy correlation methods are the most widely applicable for the variety of conditions found on large playa lakes. Chloride profiling is shown to be highly sensitive to thermal and density-driven fluxes in the near surface and, as a result, appears to underestimate yearly groundwater evaporation. Yearly mean groundwater evaporation from the playa surface estimated from the three study areas was found to range from 88 to 104 mm year⁻¹, whereas mean evaporation from the brine-covered areas was 872 mm year⁻¹. Uncertainties on these mean rates were estimated to be ±25%, based on comparisons between eddy correlation and lysimeter estimates. On a yearly basis, evaporation accounts for approximately 47 × 10⁶ m³ of water loss from the playa surface and open-water areas of the lake. Over the playa area, as much as 7.5 × 10⁸ kg (7.5 × 10⁵ t) of salt are annually concentrated by evaporation at or near the playa surface, much of which appears to be lost during dust storms in area.     

Petrogenesis and paleotectonic history of the Wild Bight Group,an Ordovician rifted island arc in central Newfoundland

The Wild Bight Group (WBG) is a sequence of early and middle Ordovician volcanic, subvolcanic and epiclastic rocks, part of the Dunnage Tectonostratigraphic Zone of the Newfoundland Appalachians. A detailed geochemical and Nd-isotopic study of the volcanic and subvolcanic rocks has been carried out to determine the geochemical characteristics of the rocks, interpret their palcotectonic environments and constrain their petrogenetic history. The lower and central stratigraphic levels of the WBG contain mafic volcanic rocks with island-arc geochemical signatures, including LREE-enriched are tholeiites with _Nd(t) =-0.1 to +2.2 (type A-I), LREE-depleted arc tholeiites with _Nd(t) =+5.6 to +7.1 (type A-II) and an unusual suite of strongly incompatible-element depleted tholeiites in which _Nd(t) ranges from-0.9 to +4.6 and is negatively correlated with¹⁴⁷Sm/¹⁴⁴Nd (type A-III). High-silica, low-K rhyolites occur locally in the central part of the stratigraphy, associated with mafic rocks of arc affinity, and have _Nd(t) =+4.7 to +5.4. The upper stratigraphic levels of the WBG dominantly contain rocks with non-arc geochemical signatures, including alkalic basalts with _Nd(t) =+4.6 to +5.5 (type N-I), strongly LREE- and incompatible element-enriched tholeiites that are transitional between alkalic and non-alkalic rocks with _Nd(t) =+4.4 to +7.0 (type N-II) and rocks with flat to slightly LREE-enriched patterns and _Nd(t) =+5.1 to +7.4 (type N-III). Rocks with non-arc and arc signatures are locally interbedded near the stratigraphic type of the WBG. Nd-isotopic data in the type A-I and A-II rocks are generally compatible with mixing/partial melting models involving depleted mantle, variably contaminated by a subducted crustally-derived sediment. The petrogenesis of type A-III rocks must involve source mixing and multi-stage partial melting, but the details are not clear. The geochemistry and Nd isotope data for types N-I, N-II and N-III rocks are compatible with petrogenetic models involving variable partial melting of a source similar to that postulated for modern oceanic island basalts. Comparison of the WBG with modern analogues suggests a 3-stage developmental model: stage 1) island-arc volcanism (eruption of type mafic volcancs); stage 2) arc-rifting (continued eruption of type A-I, A-I, eruption of types A-II and A-III mafic volcanics and high-silica, low-K rhyolites); and stage 3) back-arc basin volcanism (continued minor eruption of type A-I basalts, eruption of types N-I, N-II, N-III basalts). Stages 1 and 2 volcanism involved partial melting of subduction contaminated mantle, while stage 3 volcanism utilized depleted-mantle sources not affected by the subducting slab. This model provides a basis for interpreting coeval sequences in central Newfoundland and a comparative framework for some early Paleozoic oceanic volcanic sequences elsewhere in the Appalachian orogen.