天然水体中酚的降解动力学

本文报道了天然水体中低浓度酚的降解动力学;计算了它的降解速率常数、降解活化能等。降解半表期是t_(1/2)=1.5d~(-1)(10℃),t_(1/2)=O.74d~(-1)(30℃)。低浓度酚的降解动力学跟天然水体中酚的降解情况比较接近。本文的结果对环境评价、蓄水库工程设计等很有参考价值。     

化学发光法测定天然水体中低浓度硝酸盐和亚硝酸盐的含量

传统分光光度法测定硝酸盐和亚硝酸盐含量时检测限较高,无法测定部分海洋表层及寡营养盐海域低含量的硝酸盐和亚硝酸盐浓度,急需采用一种新的测定低浓度硝酸盐和亚硝酸盐的方法.化学发光法用于测定水体中硝酸盐和亚硝酸盐含量,具有灵敏度高、检测限低、样品用量少,不受悬浮颗粒物、有色物质影响及样品批量测定等优点.本文通过探索载气流速、...     

过氧化氢对两种海洋微藻的毒性效应研究

运用可见分光光度法,研究了不同H2O2浓度和不同作用时间对青岛大扁藻(P.helgolandica var.tsingdaoensis)和新月菱形藻(Nitzschia closterium)的毒性效应,得到了H2O2对两种藻72h的抑制率,并且在同-H2O2浓度条件下,对不同生长期和不同浓度细胞的毒性作用进行了对比。结果表明,低浓度的H2O2对微藻种群增长有微弱的促进作用,随着H2O2浓度的增加,促进作用变为抑制作用,抑制率也由负变正,并且H2O2浓度越大、作用时间越长其毒性作用越大;H2O2浓度相同时,对微藻生长的抑制作用随着细胞浓度的增大而减小,而且对稳定期细胞的抑制作用大于指数期细胞。     

海水中溶解有机磷的测定方法

磷和氮一样,都是海洋环境中的重要生源要素,其在水环境中的时空分布控制着海洋生态系统中的初级生产过程.在大洋或深海区,氮的供应相对不足常是初级生产的制约因素,但在浅海区,特别是河口和海湾,由于农业施肥、城市污水及大气干湿沉降等的作用,氮/磷比值常远高于Redfield比值,从而使磷成为初级生产的制约因素^[1-6].     

海水中天然溶解有机物在固体颗粒上的吸附

实验研究海水中天然溶解有机物（ＤＯＭ）在δ－ＭｎＯ２、粘土和二氧化硅上的吸附,海水中溶解有机碳（ＤＯＣ）在δ－ＭｎＯ２、高岭石、伊利石和二氧化硅上的吸附率随ｐＨ的增加而减小。结果表明,在天然海水ｐＨ８．１条件下,海水中天然溶解有机物在这４种固体粒子上的吸附率大小为：δ－ＭｎＯ２（３２％）＞伊利石（１４％）＞高岭石（４％）≈二氧化硅（３％）。根据统计热力学方法得到的公式能够很好地拟合海水中ＤＯＭ在固体颗粒物上的吸附。     

海洋环境中氧化还原敏感性微量元素的地球化学行为及环境指示意义

依据国内外最新研究成果,初步讨论了氧化还原敏感性微量元素(RSE)Re、Cd、Mo、U、V等的地球化学行为,其中包括海洋沉积物中RSE的来源、RSE在缺氧和无氧海区的沉淀富集机理及其环境指示意义。在此基础上讨论了利用RSE研究氧化还原环境时应注意的一些问题。RSE的沉淀富集机制不尽相同,但具有以下共同特点:①对底层海水的溶解氧浓度敏感。在正常溶解氧条件下,氧化还原敏感性微量元素在海水中呈溶解态稳定存在,而当底层海水处于缺氧或无氧条件时容易发生还原。②当底层海水处于缺氧或无氧条件时,经过沉积物—海水界面过程,受缺氧程度不同的制约,海水中呈溶解态的RSE依次在沉积物中沉淀,出现不同程度的富集。③持续还原条件下,RSE在沉积物中稳定存在;受氧化作用后,容易在沉积物中发生二次迁移和重新富集。不同的RSE其氧化还原电位不同,在氧化还原序列中的位置不同,Re在U之后Mo之前发生还原。因此,RSE在海洋沉积物中的不同富集特征和富集程度可作为还原程度指标研究底层海水的缺氧程度和底质的氧化还原环境。研究RSE的氧化还原环境指示意义,必须对RSE陆源碎屑来源组分进行剔除,同时,还应充分注意到还原沉积区发生氧化后,RSE在沉积物中会发生重新迁移和二次富集。     

厦门浔江湾水体交换的~(224)Ra和~2H示踪研究

本文研究了 980 32 6航次厦门浔江湾海水中2 2 4Ra和2 H的含量与分布 ,揭示其水体交换特征。表层水体中2 2 4Ra的放射性比度介于 4.94～ 1 3.70Bq/m3之间 ,平均值为 7.2 6Bq/m3 ;δD测值介于 - 8.9× 1 0 -3 ～ - 5 .7× 1 0 -3 之间 ,平均值为 - 7.3× 1 0 -3 。表层水2 2 4Ra和2 H的分布表明 ,浔江湾在一定程度上受到西港水的入侵 ,湾内外水体的不完全交换造成外海水在该湾中部的滞留。     

河水与海水混合过程中Eh-p H的变化特征及影响因素

河口是河水和海水混合地带,河口地区每时每刻都在发生复杂的物理、化学、生物作用,该过程中水体Eh、pH参数的变化直接关系到氧化还原元素的行为以及重金属、有机污染物的迁移、转化和清除.本研究采集了长江河水、东海陆架海水,设置了盐度为5、12.5、25的3组混合实验,模拟长江河口水体混合过程,实时测定混合过程中水体Eh、pH...     

Direct determination of surface active substances in natural waters

Advantages of direct determination of surface active substances without sample pretreatment, using the electrochemical method (a.c. polarography) based on the measurement of adsorption effects on the mercury electrode, are illustrated for a number of freshwater and marine samples and phytoplankton culture media. The effects of dilution, filtration and centrifugation of samples were investigated. A high loss of organic material through filtration was observed for selected sea surface microlayer samples and phytoplankton culture media. The samples were compared with different model surfactants and were found to possess similar adsorption characteristics to hydrophobic, fatty surfactants. The freshwater samples were found to be more stable during pretreatment than the marine samples. Humic substances are the predominant surface-active compounds in freshwater systems. The use of a calibration curve for humic material is proposed for the rapid and direct determination of surfactant activity values for freshwater samples.     

Voltammetric methods of sulfate ion analysis in natural waters

Sulfate anion can be measured in waters of widely varying salinity by polarography and amperometry. Polarography is the preferred method because it allows for measurement of sulfate in the 50-ppm range. The polarographic method is rapid, precise, and can be adapted for smaller sample volumes by simple modification of the sample preparation. We report a precision of 0.17% on I.A.P.S.O. standard seawater and 0.90% on 50-ppm samples. Amperometry requires more time overall for analyses because it is a titrimetric method, but it also is a precise technique (0.28% on I.A.P.S.O. standard seawater). Both techniques do not require any unusual sample preparation and are easily performed in most laboratories.     

The thermodynamics and kinetics of the hydrogen sulfide system in natural waters

The thermodynamics and kinetics of the H₂S system in natural waters have been critically reviewed. Equations have been derived for the solubility and ionization of H₂S in water and seawater as a function of salinity, temperature and pressure. Pitzer parameters for the interaction of the major cations (Na⁺, Mg²⁺ and Ca²⁺) with HS⁻ have been determined to allow one to calculate values of pK₁^* in various ionic media. The limited data available for the interaction of trace metals for HS⁻ are summarized and future work is suggested.The kinetics of oxidation of H₂S have also been examined as a function of pH, temperature, and salinity. The discrepancies in the available data are largely due to the different [O₂]/[HS−] ratios used in various studies. Over a limited pH range (6–8) the pseudo first order rate constant for the oxidation is shown to be directly proportional to the activity of HS⁻. Further studies are suggested to examine the effect of ionic media and temperature on the rate of oxidation.     

Photochemical production of hydrogen peroxide in Antarctic Waters

Photochemical production rates of hydrogen peroxide (H₂O₂) were determined in Antarctic waters during two research cruises. The first cruise was from mid-October to mid-November, 1993, in the confluence of the Weddell and Scotia Seas, and the second cruise was in December, 1994, along the coast of the Antarctic Peninsula. During these cruises, midday sea-surface production rates ranged from 2.1 to 9.6 nM h⁻¹, with an average rate of 4.5 nM h⁻¹. Production rates were consistently smaller than rates determined at lower latitudes (>9 nM h⁻¹), primarily due to the colder temperatures and lower ultraviolet irradiances in polar waters. In situ production rates were determined with a free-floating drifter that was deployed for 12–14 h. Production rates, averaged over the deployment time, were highest at or near the surface (ca. 2.4–3.5 nM h⁻¹) and decreased rapidly with depth to 0.1–0.7 nM h⁻¹ at 10–20 m. The decrease in production rates with depth generally paralleled the decrease in ultraviolet irradiance in the water column. Production rates of hydrogen peroxide in Antarctic seawater were largely controlled by the ultraviolet irradiance in the water column, although there was some evidence for production in the blue region of the solar spectrum. A laboratory study was conducted to determine the wavelength dependence of the apparent quantum yield for the photochemical formation of hydrogen peroxide in Antarctic waters. Apparent quantum yields determined at 0°C decreased from 0.74×10⁻³ mol einstein⁻¹ at 290 nm to 1.0×10⁻⁵ mol einstein⁻¹ 410 nm. At 20°C, apparent quantum yields for the photochemical production of hydrogen peroxide were within a factor of two of apparent quantum yields determined in temperate waters at 20–25°C. Sunlight-normalized H₂O₂ production rates were determined as a function of wavelength using noontime irradiance data from Palmer Station, Antarctica. A decrease in stratospheric ozone from 336 to 151 Dobson units resulted in a predicted 19–42% increase in the photoproduction of H₂O₂ at the sea surface in Antarctic waters. The magnitude of this increase depends on the concentration and absorbance characteristics of dissolved organic matter in the photic zone, as well as on other factors such as cloudiness and decreasing solar zenith angle that tend to lower photochemical rates offsetting increases due to stratospheric ozone depletion.     

On-line determination of silver in natural waters by inductively-coupled plasma mass spectrometry: Influence of organic matter

We investigated interference effects on the analysis of silver in estuarine and oceanic waters using on-line high resolution inductively coupled plasma mass spectrometry (ICP-MS). A mini-column packed with a strong anion exchange resin (Dowex 1-X8) was used in a flow-injection system to separate and concentrate silver from the saline samples prior to on-line determination by ICP-MS. A series of analyses showed the concentrations of silver measured in San Francisco Bay estuary and the North Pacific that had been acidified (pH < 2) and stored for periods of 1–2 years were 10–70% lower than those measured in aliquots of those samples after ultraviolet (UV) irradiation. Additional silver released after UV irradiation of the estuarine waters, but not the ocean waters, was positively correlated (r = 0.77, simple linear correlation) with chlorophyll-a concentrations, but not with dissolved organic carbon (DOC) concentrations. Spatial distributions of chlorophyll-a and UV-released silver also exhibited similar patterns along a salinity gradient in the San Francisco Bay estuary, suggesting an in situ biogenic source of the interferent for the silver measurements.     

Colorimetric determination of nanomolar concentrations of silicate in natural waters after liquid-liquid extraction using methyl isobutyl ketone

A sensitive solvent extraction method for the determination of nonamolar concentrations of silicate in natural waters is developed. According to the traditional aqueous silicate method, silicomolybdenum blue formed by the reaction between silicate and ammoni- um molydate and reduced by metol-sulfite reagent is extracted by methyl isobutyl ketone. The absorbance can be enhanced substantially up to 10-folds. The detection limit of silicate is 8 nmol/dm^3 , which is one tenth smaller than the traditional method, with the precision of 4.0% at a silicate level of 50 nmol/dm^3 and 3.2% at a silicate level of 6 μmol/dm^3. Comparing the calibration curves in the distilled water and seawater, it can be seen that the salt effect also exists in the extraction method. However, the salt effect is a linear function of the salinity and can be corrected by simple calibration. The proposed method is successfully applied to the determination of silicate in natural waters. Natural concentrations of arsenate, arsenite and phosphate cause negligible interference.     

The monosaccharide spectra of natural waters

Monosaccharides were determined in waters and sediment pore waters from a wide variety of environments and locations. Desalting was performed by electrodialysis and concentrated extracts were analyzed by two forms of liquid chromatography. At least 12 sugars were identified. Glucose and fructose were the dominant monosaccharides in nearly all samples examined. Analyses of over 150 seawater and sediment pore water samples showed that fructose is highly significantly correlated (>0.99) with glucose concentrations. Laboratory kinetic experiments on the epimerization reaction, glucose ? fructose, in sterilized natural seawater in the dark, yielded a forward rate constant, k₁, of 1.2 × 10^?5 h^?1 at 25°C and 1.6 × 10^?7 h^?1 at 2°C. The approximate time required to attain equilibrium at 25°C was 1.1 y and at 2°C, 15.4 y; the measured equilibrium constant was in the range 0.3–0.4. The actual ratio of fructose to glucose in natural water samples was usually in the range 1.0–1.4/l, independent of the total monosaccharide concentrations, which varied in the samples by a factor of ～100. Several possible explanations for the apparent discrepancy in the determined and found ratios are discussed: the presence of universal, as yet, undiscovered major biological sources for fructose in marine environments; preferential utilization of glucose; preferential incorporation of fructose into or onto inorganic colloids; and preferential formation of fructose-transition metal ion associations.     

Sources and sinks of methylgermanium in natural waters

New data have extended our understanding of the distribution and behavior of methylgermanium in the environment. Laboratory attempts to induce aerobic methylation with known biological and abiotic methylating agents were unsuccessful; this confirmed previous field observations of methylgermanium's unreactive behavior. However, biomethylation of inorganic germanium was observed in the anaerobic digestor of a sewage treatment plant, which suggested a terrestrial methanogenic source. Attempts to locate such a source in methanogenic swamps and their drainages reveal very low methylgermanium concentrations typical of other remote, pristine rivers. Polluted rivers have monomethylgermanium (MMGe) and dimethylgermanium (DMGe) concentrations 3–100 times higher than those of pristine rivers, which suggests an anthropogenic source of methylgermanium as a result of the synergistic effects of sewage treatment and coal-ash derived inorganic germanium contamination. A new high-precision profile of MMGe and DMGe in the Sargasso Sea shows conservative behavior with no vertical gradients. However, marine anoxic basins have both inorganic germanium enrichment and methylgermanium depletion, which suggests that of marine anaerobic processes are responsible for demethylating marine organogermanium. These results all suggest that methylgermanium is produced on the continents, is unreactive in the open ocean, and is destroyed in marine anoxic environments. The residence time of organogermanium in the sea, based on a continental source (pristine rivers), is at least 1 Ma, consistent with its unreactive nature, its observed distribution in the ocean, and rates of destruction in anoxic basins.     

A comparison between high temperature catalytic and persulfate oxidation for the determination of total dissolved nitrogen in natural waters

Total dissolved nitrogen(TDN) is an important parameter for assessing the nutrient cycling and status of natural waters.The accurate determination of TDN in natural waters is essential for assessing its contents and distinguishing different forms of nitrogen in the water.The TDN in various systems has been largely documented,and the concentrations of TDN are usually obtained using high-temperature catalytic(HTC) or persulfate oxidation(PO).However,the accuracy of these methods and their suitabil...