A new application of the diacetyl monoxime method to the automated determination of dissolved urea in seawater

A new application of the diacetyl monoxime method for the determination of dissolved urea in seawater is presented, based on the Alpkem autoanalyzer (OI, Analytical). This system has several advantages over automated methods previously described in the literature. The urea cartridge can be easily built using nut/ferrule connections, and the external thermostatic bath is not required. The system is set up to operate at low urea concentrations (0–3 µM urea), but it is linear up to 100 µM urea. The sample volume needed for analysis is 0.4 ml, and the rate of analysis is 25 samples h^–1. The precision of analysis (CV) of seawater samples is 2.1% at 0.50 µM urea, and the detection limit is 0.02 µM urea. The interference on the colorimetric measurement due to formation of Brij-35 aggregate in strongly acidic media was eliminated by substituting this wetting agent with hexadecyl–trimethyl–ammonium bromide; thus, this method is suitable for other autoanalyzer technologies that use small-diameter transmission tubes and small-sized spectrophotometric flowcells.Communicated by R. Cattaneo-Vietti, Genova     

厦门西海域典型站位二甲基硫化物的周日变化初探

采用顶空-固相微萃取-气相色谱分析,探讨了厦门西海域某典型站位表层海水中二甲基硫(DMS)、二甲基巯基丙酸(DMSP)以及二甲基亚砜(DMSO)含量的周日变化规律.结果表明,DMS、总DMSP(DMSPt)、颗粒态DMSP(DMSPp)、溶解态DMSP(DMSPd)均呈现出白天高、夜晚低的变化规律,与浮游生物昼夜活性的变化直接相关,DMSO则没有明显的变化规律.浮游植物优势种和浮游植物生物量明显影响DMS,DMSPt,DMSPp和DMSPd的浓度,未见其对DMSO的影响.DMS,DMSPt和DMSPd的浓度与叶绿素a的浓度有较好的相关性.突如其来的暴雨使表层海水中DMS和DMSP的浓度显著增加,亦未见其对DMSO影响.海水中的盐度和硝酸盐浓度与DMS,DMSP和DMSO浓度的周日变化均不相关.     

北京市场常见水产品中总汞、甲基汞分布特征及食用风险

以甲苯二次萃取-直接测汞的方法对北京市场常见水产品中的甲基汞进行分析测定,并评价了食用人群的暴露风险。分析样品包括大黄鱼（Pseudosciaena crocea）、虾（Penaeus chinensis）等9种常见海产品以及武昌鱼（Megalobrama amblycephala Yih）、鳙鱼（Aristichthys nobilis）2种淡水海产品。测定结果表明：海产品中总汞和甲基汞质量分数要远高于淡水鱼中的总汞和甲基汞质量分数,总汞绝大多数是以甲基汞的形式存在,所占比例从74.7%到96.0%不等;对其中3种鱼类的鱼体甲基汞分布研究表明：肌肉中的甲基汞质量分数最高,肝脏中次之,鱼鳃中质量分数最低。根据我国水产品甲基汞标准,本研究中水产品甲基汞质量分数均低于国家标准,但根据世界卫生组织（WHO）和美国环保署EPA颁布的甲基汞摄入量参考值,食用银鳕鱼等甲基汞质量分数相对较高的水产品仍然存在一定的风险,应注意限量。     

Decomposition of urea associated with photosynthesis of phytoplankton in coastal waters

Decomposition of urea in seawater was studied in Mikawa Bay, a shallow eutrophic bay on the southern coast of central Japan. The urea concentration in seawater ranged from 1.3 to 5.9 μg-at. N/1 and comprised 12 to 40% of the dissolved organic nitrogen. Using ¹⁴C labelled urea, the rate of CO₂ liberation from urea and the incorporation rate of urea carbon into the particulate organic matter were determined. For the surface samples, high rates of CO₂ liberation from urea as well as the incorporation of urea carbon into the particulate organic matter were observed in the light, while much lower rates were obtained in the dark. Incubation experiments with exposure to different light intensities revealed that the rate of CO₂ liberation from urea and the incorporation of urea carbon into particulate organic matter changed with light intensity, showing a pattern similar to that of photosynthesis. The highest liberation and incorporation rates were observed at 12,000 lux. Incubation in light and in dark produced marked decreases and increases, respectively, in urea and ammonia, while no appreciable changes were observed for nitrate and nitrite. It is suggested that urea decomposition associated with photosynthetic activity of phytoplankton is one of the major processes of urea decomposition, and that it plays a significant role in the nitrogen supply for phytoplankton in coastal waters.     

疏浚对大连湾生物可利用磷的水体浓度和沉积物-水界面交换通量的影响

利用FeO/CAM复合膜对大连湾已疏浚区与疏浚影响区海水水体中生物可利用磷(Bio-available phosphorus,BAP)浓度和水质指标进行调查,并通过实验室培养法、间隙水浓度梯度估算法和薄膜扩散梯度技术(Diffusivegradients in thin films technique,DGT)法分别测定沉积物-水界面间BAP交换通量.结果表明,由于受到调查海区附近正在进行的疏浚工程的影响,疏浚影响区水体中浊度和悬浮物含量平均值高于已疏浚区,且疏浚影响区水体中BAP的平均浓度(22.2μg L-1)高于已疏浚水体(19.5μg L-1);而疏浚影响区叶绿素a和溶解氧的浓度明显低于已疏浚区.沉积物-水界面间BAP交换通量研究结果显示,BAP主要由沉积物向上覆水中扩散,沉积物是BAP交换的源;间隙水浓度梯度估算法和DGT法测定的BAP交换通量相似,但远低于实验室培养法测定值;BAP在已疏浚区沉积物-水界面间的交换通量小于疏浚影响区,说明在一定时间内疏浚可以减弱沉积物内源磷的释放.     

Headspace and small-chamber studies of airborne diacetyl release from selected food flavoring mixtures: activity coefficients and air modeling implications

Laboratory studies were conducted to evaluate airborne release of diacetyl from selected mixtures simulating butter flavorings added to foods. The test materials included diacetyl (97% purity); 0.015%, 0.15%, 1.5%, and 3.0% diacetyl in a water/propylene glycol mixture; 1.5% diacetyl in deionized water or soybean oil; and 3% or 6% diacetyl in a commercial steam distillate from milk fermentation known as “butter starter distillate.” Diacetyl was quantified by gas chromatography with flame ionization detection. Expected concentration-dependent emission patterns based on liquid diacetyl content were demonstrated, but were significantly altered by mixture composition. Soybean oil and deionized water more readily released diacetyl when compared with starter distillate, propylene glycol solutions, and pure diacetyl. Measured diacetyl concentrations under static headspace and dynamic flow-chamber conditions were compared to estimated concentrations utilizing Raoult's law with published and fitted activity coefficient corrections for each mixture, indicating that published coefficients often understated the measured concentrations. It is concluded that headspace (static) and small-chamber (dynamic) measurements of airborne diacetyl provide data to assist in validating model-estimated airborne diacetyl concentrations by using mixture-specific activity coefficients. Implications of these empirical data for validating exposure estimates for diacetyl based on near-field/far-field modeling in workplace settings are discussed.     

Methodology and measurement of adenylate energy charge ratios in environmental samples

A method for measuring ATP, ADP and AMP levels in environmental samples was devised, and applied to seawater and bacterial cell extracts. This procedure is specifically designed for measuring the extremely low concentrations of total adenine nucleotides ([A_T]=[ATP]+[ADP]+[AMP]) that are apt to occur in most natural ecosystems (i.e., 10 ng A_T ml^-1 of sample extract). Although the current assay methodology can be used with purified firefly luciferase reagents, it has been suitably modified to accept crude luciferase preparations as well. ATP, ADP and AMP levels have been measured, and the corresponding energy charge (EC) ratios determined for seawater samples collected off the Southern California coast. The EC ratios ranged from 0.50 to 0.89, with peak values corresponding to the subsurface maxima in ATP and chlorophyll a concentrations, and the minimum values corresponding to the deepest water sampled (1500 m). The measurement of adenylate energy charge ratios in environmental samples can be a useful indicator of mean community metabolic activity and potential for cell growth.     

Analysis of volatile fatty acids by ion-exclusion chromatography,with special reference to marine pore water

A method for measuring volatile fatty acids using ion-exclusion chromatography is presented. The system was found to be applicable to samples with high salt concentrations (e.g. seawater and marine pore water) when coupled with a vacuum distillation procedure. The method is straightforward, with no sample preconcentration and no introduction of external contamination. Calibration was found to be linear, with good reproducibility (coefficient of variation normally less than 5%) and the system was sufficiently sensitive to operate at the sub-ppm level (minimum detection limit for acetate and propionate was approximately 0.02 and 0.05 ppm, respectively). This technique was used to investigate the distribution of volatile fatty acids with sediment depth at Station E70 in Loch Eil, Scotland (sample was collected in March, 1983) and the results were in good agreement with recent publications. Although the system, at present, is limited in marine pore water to acetate and propionate, it has certain advantages over alternative systems and these are described.     

Characteristics of suspensions of Kuwait oil and Corexit 7664 and their short-and long-term effects on Tisbe bulbisetosa (Copepoda: Harpacticoida)

A technique for preparing seawater suspensions of Kuwait oil and Corexit was developed. The resulting hydrocarbon concentrations were analysed by gas-chromatography and spectrofluorometric methods and the stability of the suspensions with time was determined. It was established that the suspensions have an effective stability from Days 3 to 15 after preparation, since in this period the concentration varies within a relatively narrow range. Adult female Tisbe bulbisetosa appeared to be quite tolerant of this type of hydrocarbon suspension, in short-term experiments, especially considering that the concentrations used in the bioassays were about 200 times higher than those measured in a relatively polluted area of the lagoon of Venice. Long-term effects on number of eggs produced, number of nauplii and hatching success for females of the third and fourth generations, subject to continuous exposure, were negligible compared with controls.     

Variation in urea excretion in the gulf toadfishOpsanus beta

Under long-term (24 h) control measurements, significant urea was excreted (15 to 90% of excreted nitrogen) byOpsanus beta (Goode and Bean) collected in 1989 from Biscayne Bay, Florida, USA. Urea excretion rates and plasma urea concentrations were not affected by antibiotic treatments which decreased intestinal microbe populations. These results suggest that nitrogen recycling by gut microbe urease is probably not significant in this species. Urea excretion rates increased significantly following 8 h of air-exposure and in response to high levels of NH₄Cl. These results suggest that urea is synthesized and excreted by the toadfish primarily in situations that limit ammonia excretion. Thus, the ornithineurea cycle in the toadfish liver primarily maintains low concentrations of ammonia within the fish. High levels of variability in urea excretion rates and variation in response to air-exposure suggest that urea synthetic rates are affected by immediate past environmental conditions.     

The kinetics and possible significance of nitrate uptake by several algal-invertebrate symbioses

Nitrification in the coral reef community at Lizard Island, Great Barrier Reef, Australia, elevated the nitrate concentration to above that of the nearby open ocean water. Reef corals and a zooxanthellae-bearing foraminiferan were shown to take up nitrate from nitrate-enriched seawater; a lag period was absent, indicating that the responsible enzymes did not require induction. The relationship of nitrate uptake to seawater nitrate concentration could be described by a hyperbola with a non-zero intercept on the abscissa. Corals are opportunistic in acquiring nitrogen; in addition to gaining particulate nitrogen from ingested food, they acquire dissolved nitrogen in the form of nitrate, ammonia and urea.     

Chemometric studies of water quality parameters of Sankarankovil block of Tirunelveli, Tamilnadu

The fluoride concentration in ground water was determined in Sankarankovil block of Tirunelveli district of Tamilnadu (India) where it is the only source of drinking water. Various other water quality parameters such as pH, electrical conductivity total hardness and total alkalinity as well as calcium, magnesium, carbonate, bicarbonate and chloride concentrations were also measured. A systematic calculation of correlation coefficient among different physico-chemical parameters was performed. The analytical results indicated considerable variations among the analyzed samples with respect to their chemical composition. Majority of the samples do not comply with Indian as well as WHO water quality standards. The fluoride concentration in the ground water of these villages varied from 0.66 to 3.84 mg l(-1), causes dental fluorosis among people especially children of these villages. The high and low fluoride containing areas were located using isopleth mapping technique. Overall water quality was found unsatisfactory for drinking purposes without any prior treatment except at few locations out of 50 villages.     

近岸海水中全氟化合物的液相色谱-离子阱质谱法测定

建立了利用高效液相色谱-电喷雾离子阱质谱(HPLC-ESI-IT-MS/MS)测定近岸海水中多种常见全氟化合物(PFCs)的分析方法.采用固相萃取法(SPE)对海水中的PFCs净化富集,用HPLC-ESI-IT-MS/MS多反应离子监测(MRM)模式对各组分(全氟己烷磺酸、全氟辛烷磺酸、全氟辛烷磺酰胺、全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟癸酸、全氟十一酸、全氟十二酸)进行测定.在最佳实验条件下,采用基质匹配标准曲线法定量,以消除海水基质的影响,8种目标化合物的检出限介于0.50—1.00 ng·L-1,9种PFCs的回收率在71.0%—130.2%之间,能满足近岸海水中多种PFCs检测的要求.青岛沿岸表层海水样品测定结果显示,全部采样站点的海水样品中均检测到≥4种PFCs,说明青岛沿岸海水中已有一定程度的PFCs污染.     

不同培养介质中纳米氧化铜对小麦毒性的影响（Influence of Culture Media on the Phytotoxicity of CuO Nanoparticles to Wheat（Triticum aestivum L.））

通过比较纳米氧化铜(CuONPs)和微米氧化铜(CuOMPs)在两种土壤中Cu2+的溶出及其对脲酶活性影响,结合产生脲酶活性抑制效应的Cu2+浓度阈值,研究了CuONPs和CuOMPs对土壤脲酶活性的毒性效应机制.结果表明:CuONPs和CuOMPs的Cu2+溶出量随其浓度增加而增加,溶出比率随浓度增加而减少,两者在红壤中Cu2+的溶出均比在乌栅土中高;在1～1000mg·kg-1范围内,CuONPs对土壤脲酶活性产生了显著(p≤0.05)或极显著(p≤0.01)的抑制效应;同浓度下,CuONPs在土壤中的Cu2+溶出及其对脲酶活性的抑制效应均大于CuOMPs;在相对低浓度(1～10mg·kg-1,红壤;1～100mg·kg-1,乌栅土)下,CuO的纳米态对土壤脲酶活性具有抑制毒性,在相对高浓度(≥50mg·kg-1,红壤;≥500mg·kg-1,乌栅土)下,CuO的纳米态和溶出Cu2+共同作用引起了脲酶活性抑制;与CuONPs不同,CuOMPs只有通过溶出Cu2+抑制土壤脲酶活性,其颗粒态对脲酶活性无显著影响;值得注意的是,在低浓度(1mg·kg-1)下CuONPs对土壤脲酶活性具有微米态和离子态所没有的抑制毒性,说明其对土壤酶影响应存在特殊机理,值得进一步深入研究.     

Effects of temperature,seawater osmolality and season on oxygen consumption and osmoregulation of the amphipod Gammarus oceanicus

Seasonal variations of oxygen consumption rate, haemolymph osmolality and the concentrations of the inorganic ions potassium and sodium in the haemolymph were measured in the littoral amphipod Gammarus oceanicus collected from the Trondheimsfjorden, Norway in 1987. For each season comparisons were made of amphipods acclimated for 1 wk to 0.5, 4.5, 10.0, 15.0 and 20.0°C, in combination with seawater osmolalities of 100, 500 and 1200 mOsm and to the seawater osmolality corresponding to that of the collecting site. The oxygen consumption rate showed a temperature insensitivity when the amphipods were acclimated to low temperatures in winter and high temperatures in summer. Significant differences were found in oxygen consumption between individuals acclimated to various medium osmolalities, possibly indicating higher energy requirements for osmotic and ionic regulation at low seawater osmolalities. Oxygen consumption rate was significantly higher in summer than in other seasons. Haemolymph osmolality and the concentration of the inorganic ions sodium and potassium were not influenced by temperature or season. Determination of haemolymph osmolalities and concentrations of inorganic ions revealed that G. oceanicus is a strong hyper-osmotic and hyper-ionic regulator in dilute seawater. The concentration of potassium in the haemolymph is less influenced by seawater osmolality than haemolymph osmolality and the haemolymph concentration of sodium.     

Variability of nitrate concentration in nitrogen-depleted subtropical surface waters

Recent improvements in the analytical determination of nitrate and nitrite allow measurements of nanomolar concentrations in nitrogen-depleted surface waters, revealing variability not previously observable. The new methods allow direct observation of net nitrate consumption and production measured as changes in nitrate concentration over time in incubated samples of seawater. We find that nitrate concentrations in nitrogendepleted surface waters show regional differences, and sometimes diel differences. The variability in nitrate concentration reflects differences in atmospheric inputs, in physical forcing, as well as in the biological processes of nitrate uptake and nitrification. Examples are shown from the Southern California Bight (1986–1987), the equatorial Pacific (February–March, 1988), and the eastern subtropical Atlantic (March–April, 1989).     

渤海北部典型芳香烃类化合物污染状况及生态风险评价

为探究渤海北部海上油气区及周边近岸海域典型芳香烃类化合物污染状况,2015年5月现场采集了32个站位的海水样品,针对7种苯系物(BTEX)和17种多环芳烃(PAHs)进行测定,并采用商值法和毒性当量法对污染物开展单一和联合生态风险评估。结果显示,研究海域海水中7种苯系物总含量范围为65.1～222.6 ng·L~(-1),以甲苯含量最高,表层含量略低于底层,油气区平均含量低于周边近岸,受到陆源污染输入的影响特征明显。表层海水中ΣPAHs含量范围为98.9～356.0 ng·L~(-1),平均值为184.5 ng·L~(-1),以低环芳烃占优势,总体处于中等水平,比值法判定该海域PAHs可能主要来源于石油及其加工产品。该海域海水中苯并(a)芘的风险商RQ值大于0.1,表现出低度风险,其余3种处于可接受水平。4种芳香烃类化合物联合生态风险等级为低度风险,对生态系统具有潜在的不利影响,但不同区域仍存在一定差异性,海上石油开采与陆源输入是影响该海域个别区域生态风险较高的重要因素。     

Distribution and bioaccumulation of organochlorine pesticides along the Black Sea coast

Sediment, mussel, and seawater samples were collected three times during 2001–2003 at nine sampling stations along the mid-Black Sea coast of Turkey. The samples were analyzed with GC-ECD for contents of various organochlorine pesticides (OCPs) in the environment. DDT and its metabolites were detected at concentrations significantly above the detection limits. The highest concentrations of DDT metabolites measured in the sediment and mussel samples were 35.9 and 14.0 ng/g wet weight respectively. Considerable levels of aldrin, dieldrin, endrin, heptachlor epoxide, lindane, endosulfan sulphate, and HCB were also detected in the sediment, mussel, or seawater samples. Although these persistent toxic compounds have been banned for some years in Turkey, they may still be used illegally in some regions, contributing to their significant levels in the environment. The biota–sediment accumulation factor (BSAF) estimated for DDT and its metabolites in mussels was 2.9, which is nearly two times higher than the benchmark of 1.7. In spite of such high BSAF values observed for these toxic compounds, their levels in mussels were significantly below the international legal limits recommended by the Food and Agriculture Organization of the United Nations. Edible biota from the waterbodies examined may thus still be considered safe for human consumption at this time. However, as pollutants can biomagnify through the food chain over time, further routine sampling and analysis of biota along the Black Sea coast are warranted in order to better assess the threat of OCPs to public health in the region.     

Significance of cellular nitrate content in natural populations of marine phytoplankton growing in shipboard cultures

Phytoplankton intracellular nitrate concentrations have been monitored in a 56-h experiment on a shipboard culture of surface sea water from an upwelling region. These measurements were related to parameters of biomass (particulate nitrogen) and nitrate assimilation using the ¹⁵N isotope technique and the nitrate reducase (NR) assay. The procedure for measuring cellular nitrate concentrations is described. This parameter exhibited diurnal variations, ranging from 3.1 to 20.6 ng-at nitrate per g-at particulate nitrogen, and could be correlated positively with NR activity. Nitrogen budgets show that NR activity represents only 12% of nitrate incorporation in organic phytoplankton material when nitrate is available in the sea water. However, upon depletion of the environmental nitrate (zero uptake), NR activity can fully account for the decrease of internal nitrate. From the results, it seems that internal nitrate content is a better index of nitrate consumption by marine phytoplankton than the external concentration of nitrate-nitrogen.     

废塑料资源化产品对土壤中过氧化氢酶和脲酶活性的影响(Effect of Waste Plastics Recycling Products on Activities of Soil Catalase and Urease)

为探讨废塑料资源化产品对土壤酶活性的影响,通过室内培养试验研究了废塑料资源化产品暴露后土壤中过氧化氢酶和脲酶活性的变化.结果表明:废塑料资源化产品对土壤酶活性具有显著影响.250mg·kg-1、1250mg·kg-1、7250mg·kg-1废塑料资源化产品浓度处理对土壤中过氧化氢酶和脲酶影响明显不同.在土壤培养l～5d内,添加废塑料资源化产品的3个浓度处理土壤中过氧化氢酶活性显著低于对照(p<0.05),表现出明显的抑制作用,且浓度越高抑制作用越强.而后(5～35d),低浓度(250mg·kg-1)废塑料资源化产品对土壤过氧化氢酶一直表现为激活作用,但是,高浓度(1250mg·kg-1和7250mg·kg-1)处理对土壤过氧化氢酶活性则表现为激活-抑制-激活作用,且抑制、激活程度与处理浓度成呈相关.3个废塑料资源化产品浓度处理对脲酶活性影响在培养1～28d内主要是激活作用,且激活作用随着处理浓度的增大而增强,而后(28～35d)对脲酶活性表现为抑制作用.