Atmospheric chemistry of hydrogen fluoride

Although a large volume of monitoring and computer simulation data exist for global coverage of HF, study of HF in the troposphere is still limited to industry whose primary interest is the safety and risk assessment of HF release because it is a toxic gas. There is very limited information on atmospheric chemistry, emission sources, and the behavior of HF in the environment. We provide a comprehensive review on the atmospheric chemistry of HF, modeling the reactions and transport of HF in the atmosphere, the removal processes in the vertical layer immediately adjacent to the surface (up to approximately 500 m) and recommend research needed to improve our understanding of atmospheric chemistry of HF in the troposphere. The atmospheric chemistry, emissions, and surface boundary layer transport of hydrogen fluoride (HF) are summarized. Although HF is known to be chemically reactive and highly soluble, both factors affect transport and removal in the atmosphere, the chemistry can be ignored when the HF concentration is at a sufficiently low level (e.g., 10 ppmv). At a low concentration, the capability for HF to react in the atmosphere is diminished and therefore the species can be mathematically treated as inert during the transport. At a sufficiently high concentration of HF (e.g., kg/s release rate and thousands of ppm), however, HF can go through a series of rigorous chemical reactions including polymerization, depolymerization, and reaction with water to form molecular complex. As such, the HF species cannot be considered as inert because the reactions could intimately influence the plume’s thermodynamic properties affecting the changes in plume temperature and density. The atmospheric residence time of HF was found to be less than four (4) days, and deposition (i.e., atmosphere to surface transport) is the dominant mechanism that controls the removal of HF and its oligomers from the atmosphere. The literature data on HF dry deposition velocity was relatively high compared to many commonly found atmospheric species such as ozone, sulfur dioxide, nitrogen oxides, etc. The global average of wet deposition velocity of HF was found to be zero based on one literature source. Uptake of HF by rain drops is limited by the acidity of the rain drops, and atmospheric particulate matter contributes negligibly to HF uptake. Finally, given that the reactivity of HF at a high release rate and elevated mole concentration cannot be ignored, it is important to incorporate the reaction chemistry in the near-field dispersion close to the proximity of the release source, and to incorporate the deposition mechanism in the far-field dispersion away from the release source. In other words, a hybrid computational scheme may be needed to address transport and atmospheric chemistry of HF in a range of applications. The model uncertainty will be limited by the precision of boundary layer parameterization and ability to accurately model the atmospheric turbulence.     

Multi-Source Emission Determination Using an Inverse-Dispersion Technique

Inverse-dispersion calculations can be used to infer atmospheric emission rates through a combination of downwind gas concentrations and dispersion model predictions. With multiple concentration sensors downwind of a compound source (whose component positions are known) it is possible to calculate the component emissions. With this in mind, a field experiment was conducted to examine the feasibility of such multi-source inferences, using four synthetic area sources and eight concentration sensors arranged in different configurations. Multi-source problems tend to be mathematically ill-conditioned, as expressed by the condition number κ. In our most successful configuration (average κ = 4.2) the total emissions from all sources were deduced to within 10% on average, while component emissions were deduced to within 50%. In our least successful configuration (average κ = 91) the total emissions were calculated to within only 50%, and component calculations were highly inaccurate. Our study indicates that the most accurate multi-source inferences will occur if each sensor is influenced by only a single source. A “progressive” layout is the next best: one sensor is positioned to “see” only one source, the next sensor is placed to see the first source and another, a third sensor is placed to see the previous two plus a third, and so on. When it is not possible to isolate any sources κ is large and the accuracy of a multi-source inference is doubtful.     

小白洋淀水-沉积物系统多环芳烃的分布、来源与生态风险

以端村小白洋淀为研究对象,利用GC-MS测定了6个样点水、悬浮物和沉积物中15种优控多环芳烃(PAHs)的含量,分析了其组成与来源特征,探讨了不同多环芳烃单体的生态风险,结果表明:(1)15种优控多环芳烃的总含量(PAH15),水相为40.1-74.0ng/L,算术均值51.0ng/L;悬浮物为2438.0-5927.0ng/g,算术均值4528ng/g;沉积物为466.9-1366.4ng/g,算术均值为755.6ng/g;与国内外有关研究相比,污染较轻,(2)三相中均以2、3环PAHs为主,其比例均高于80%;并且,从水相、悬浮物相到沉积物相,2环PAHs依次降低,3环、4环依次升高,高环检出率和含量也依次升高,(3)沉积物中多环芳烃的来源以生物质燃料(秸秆、薪材)和煤的燃烧为主,以液体化石燃料(汽油、柴油和原油)的燃烧为辅,(4)沉积物中的芴(FLO)、菲(PHE)含量在潜在生态风险效应区间低值(ERL)与中值(ERM)之间,其生态风险几率介于10%-50%之间;其他PAHs单体的含量均低于ERL,其生态风险几率均低于10%.     

How effective is the new generation of GPM satellite precipitation in characterizing the rainfall variability over Malaysia?

We investigated the potential of the new generation of satellite precipitation product from the Global Precipitation Mission (GPM) to characterize the rainfall in Malaysia. Most satellite precipitation products have limited ability to precisely characterize the high dynamic rainfall variation that occurred at both time and scale in this humid tropical region due to the coarse grid size to meet the physical condition of the smaller land size, sub-continent and islands. Prior to the status quo, an improved satellite precipitation was required to accurately measure the rainfall and its distribution. Subsequently, the newly released of GPM precipitation product at half-hourly and 0.1° resolution served an opportunity to anticipate the aforementioned conflict. Nevertheless, related evidence was not found and therefore, this study made an initiative to fill the gap. A total of 843 rain gauges over east (Borneo) and west Malaysia (Peninsular) were used to evaluate the rainfall the GPM rainfall data. The assessment covered all critical rainy seasons which associated with Asian Monsoon including northeast (Nov. - Feb.), southwest (May - Aug.) and their subsequent inter-monsoon period (Mar. - Apr. & Sep. - Oct.). The ability of GPM to provide quantitative rainfall estimates and qualitative spatial rainfall patterns were analysed. Our results showed that the GPM had good capacity to depict the spatial rainfall patterns in less heterogeneous rainfall patterns (Spearman’s correlation, 0.591 to 0.891) compared to the clustered one (r = 0.368 to 0.721). Rainfall intensity and spatial heterogeneity that is largely driven by seasonal monsoon has significant influence on GPM ability to resolve local rainfall patterns. In quantitative rainfall estimation, large errors can be primarily associated with the rainfall intensity increment. 77% of the error variation can be explained through rainfall intensity particularly the high intensity (> 35 mm d^-1). A strong relationship between GPM rainfall and error was found from heavy (~35 mm d^-1) to violent rain (160 mm d^-1). The output of this study provides reference regarding the performance of GPM data for respective hydrology studies in this region.     

Seasonal change in body length of important small copepods and relationship with environmental factors in Jiaozhou Bay,China

Differences among species in prosome length and in species’ response to environmental factors do exist. Therefore, it is useful to examine prosome length for different copepod species in variable environments. Seasonal variations in prosome length of four small copepods and their copepodite stages in the Jiaozhou Bay were compared and the relative influence of temperature, salinity, and chlorophyll concentration were examined. Two peaks were found in the mean prosome length of Paracalanus parvus (in early winter and May). For Acartia bifilosa, the maximum values of all copepodites occurred mainly from February to April, and decreased to the bottom in July. Prosome length of Acartia pacifica peaked when it first appeared in June, then reached to the minimum in July. Parvocalanus crassirostris only appeared from late summer to autumn and the mean prosome length showed no clear changes. Correlations of adult prosome length with environmental factors were evaluated. For the four species, temperature was negatively correlated to prosome length except for P. crassirostris. But the different species varied markedly in their responds to temperature. A. bifilosa showed a more definite trend of size variation with temperature than P. parvus and A. pacifica. Correlations of prosome length with salinity were significantly positive for almost all the small copepods. The relationship between chlorophyll concentration and prosome length was complicated for these copepods, but for P. parvus, chlorophyll concentration was also an important affecting factor. Furthermore, investigation needs to be done on food quality for some copepod. These results are essential to estimate the biomass and the production, and to understand these small copepods’ population dynamics in this human-affected bay.     

A sulfotransferase specific to N-21 of gonyautoxin 2/3 from crude enzyme extraction of toxic dinoflagellate Alexandrium tamarense CI01

Sulfotransferase (ST) is the first enzyme discovered in association with paralytic shellfish poisoning (PSP) toxin biosynthesis in toxic dinoflagellates. This study investigates the ST activity in crude enzyme extraction of a toxic dinoflagellate species, Alexandrium tamarense CI01. The results show that crude enzyme can transfer a sulfate group from 3’-phosphoadenosine 5’-phosphosulfate (PAPS) to N-21 in the carbamoyl group of gonyautoxin 2/3 (GTX2/3) to produce C1/C2, but is inactive toward STX to produce GTX5. The crude enzyme is optimally active at pH 6.0 and 15°C. The activity is enhanced by Co2 , Mg2 , Mn2 and Ca2 individually, but is inhibited by Cu2 . Moreover, the activity shows no difference when various sulfur compounds are used as sulfate donors. These results demonstrate that the ST specific to GTX2/3 is present in the cells of A. tamarense CI01 and is involved in PSP toxin biosynthesis. In addition, the ST from different dinoflagellates is species-specific, which explains well the various biosynthesis pathways of the PSP toxins in toxic dinoflagellates.     

A Case study of a snowstorm at the Great Wall Station,Antarctica

A case of a snowstorm at the Great Wall Station was studied using data of NCEP (National Centers for Environmental Prediction) analysis, in situ observations and surface weather charts. The storm occurred on August 29th,2006, and brought high winds and poor horizontal visibility to the region.It was found that the storm occurred under the synoptic situation of a high in the south and a low in the north. A low-level easterly jet from the Antarctic continent significantly decreased the air temperature and humidity.Warm air advection at high level brought sufficient vapor from lower latitudes for the snowstorm to develop.The dynamic factors relating to strong snowfall and even the developmentof a snowstorm were deep cyclonic vorticity at middle and low levels,the configuration of divergence at high level and convergence at low level, and strong verticaluplift. There was an inversion layer in the low-level atmosphere during the later phase of the storm.This vertical structure of cold air at low levels and warm air at high levels may have been important to the longevity of the snowstorm.     

Consistent seasonal snow cover depth and duration variability over the Western Himalayas (WH)

Precipitation in solid form, i.e., snow, during winter season over the Western Himalayas (WH) leads to the build-up of seasonal snow cover. Seasonal snow cover build-up (snow cover depth and duration) largely depends on atmospheric variables such as temperature, precipitation, radiation, wind, etc. Integrated (combined) influence of atmospheric variables on seasonal snow cover gets reflected in terms of spatial and temporal variability in seasonal snow cover build-up pattern. Hence spatial and temporal variability of seasonal snow cover build-up can serve as a good indicator of climate change in high altitude mountainous regions like the WH. Consistent seasonal snow cover depth and duration, delay days and early melt days of consistent seasonal snow cover at 11 stations spread across different mountain ranges over the WH were analyzed. Mean, maximum and percentiles (25th, 50th, 75th, 90th and 95th) of consistent seasonal snow cover depth and duration show decline over the WH in the recent past 2–3 decades. Consistent seasonal snow cover is found to melt early and snow cover build-up pattern is found to show changes over the WH. Decline in consistent seasonal snow cover depth, duration and changing snow cover build-up pattern over the WH in recent decades indicate that WH has undergone considerable climate change and winter weather patterns are changing in the WH.