2010 年中国东海夏季游离态2-苯基乙胺、腐胺、亚精胺和精胺的分布

采用高效液相色谱法测定了2010年6月东海海水中的腐胺、精胺、亚精胺、2-苯基乙胺四种游离态多胺。结果表明,腐胺的浓度最高,为5.16～62.28 nmol/L,占总组成的比例为62%±15%;亚精胺的浓度最低,为0~6.98 nmol/L,占总组成的比例为6%±5%。从大面分布看,四种多胺在长江口和杭州湾附近浓度大都较高;从断面垂直分布看,2-苯基乙胺、亚精胺和精胺在大多数断面的中层浓度均高于底层浓度,腐胺在大多数断面的底层浓度高于表层浓度。夜光藻赤潮爆发处多胺的浓度相对较高。     

多胺对3株硅藻生长的影响

为探究多胺对硅藻生长的影响,以精胺、亚精胺、腐胺、尸胺和苯乙胺为外源多胺,对角毛藻Chaetoceros sp.、小新月菱形藻Phaeodactylum tricornutum Bohlin以及威氏海链藻Conticribra weissflogii进行室内添加培养。结果表明:同一温度下,不同多胺对不同硅藻生长存在特异性差异。亚精胺对角毛藻的生长起促进作用;尸胺对小新月菱形藻起促生长作用,而精胺对小新月菱形藻起抑生长作用;多胺对威氏海链藻生长前期(13 d前)主要起促生长作用,后期起抑生长作用(13 d后)。因此,适时适量添加多胺可有效促进硅藻的生长,提高硅藻的繁殖效率。     

The distribution and preferential biological uptake of cadmium at 6°W in the Southern Ocean

The spatial and temporal distribution of cadmium (Cd) and phosphate in the Southern Ocean are related to biology and hydrography. During a period of 18 days between transects 5/6 and 11, a phytoplankton spring bloom developed in the Polar Frontal region. Upper water Cd concentrations were not depleted and ranged from 0.2 to 0.8 nM at about 10 m depth. These relatively high Cd concentrations are attributed to upwelling of Upper Circumpolar Deep Water (0.5–1.2 nM in the core) in combination with low biological productivity (0.2 to 0.3 mg m⁻³ chlorophyll-a, 0.3 g C m⁻² d⁻¹). Total particulate Cd concentrations at 40 m depth were between 0.02 and 0.14 nM with the maximum in concentration in the Polar Frontal region. Most of the particulate Cd at this depth (85–94%) was detected in the first phase of a sequential chemical leaching treatment which includes adsorbed Cd as well as Cd incorporated in algae. The Polar Frontal region was characterized by minima in Cd concentration and Cd/phosphate ratio of seawater at both transects; values were the lowest at transect 11 after development of the spring bloom which was dominated by diatoms. This decreasing Cd/phosphate ratio in seawater during spring bloom development was attributed to preferential Cd gross uptake which more than compensated the process of preferential Cd recycling. Within the Upper Circumpolar Deep Water, Cd showed a maximum in concentration similar to that of the major nutrients. Both the Cd concentration and the Cd/phosphate ratio of the deeper water increased in southern direction, from 0.4 to 0.7 nM and from 0.2 to 0.3 nM/μM, respectively. Antarctic Intermediate Water has a Cd concentration of 0.21 nM with a Cd/phosphate ratio of 0.10 nM/μM. In Antarctic Bottom Water, Cd concentrations ranged from 0.60 to 0.82 nM.     

Dimethylsulphide and dimethylsulphoniopropionate in Antarctic sea ice and their release during sea ice melting

This study presents concentrations of dimethylsulphide (DMS) and its precursor compound dimethylsulphoniopropionate (DMSP) in a variety of sea ice and seawater habitats in the Antarctic Sea Ice Zone (ASIZ) during spring and summer. Sixty-two sea ice cores of pack and fast ice were collected from twenty-seven sites across an area of the eastern ASIZ (64°E to 110°E; and the Antarctic coastline north to 62°S). Concentrations of DMS in 81 sections of sea ice ranged from < 0.3 to 75 nM, with an average of 12 nM. DMSP in 60 whole sea ice cores ranged from 25 to 796 nM and showed a negative relationship with ice thickness (y = 125x^− 0.8). Extremely high DMSP concentrations were found in 2 cores of rafted sea ice (2910 and 1110 nM). The relationship of DMSP with ice thickness (excluding rafted ice) suggests that the release of large amounts of DMSP during sea ice melting may occur in discrete areas defined by ice thickness distribution, and may produce ‘hot spots’ of elevated seawater DMS concentration of the order of 100 nM. During early summer across a 500 km transect through melting pack ice, elevated DMS concentrations (range 21–37 nM, mean 31 nM, n = 15) were found in surface seawater. This band of elevated DMS concentration appeared to have been associated with the release of sea ice DMS and DMSP rather than in situ production by an ice edge algal bloom, as chlorophyll a concentrations were relatively low (0.09–0.42 μg l^− 1). During fast ice melting in the area of Davis station, Prydz Bay, sea ice DMSP was released mostly as extracellular DMSP, since intracellular DMSP was negligible in both hyposaline brine (5 ppt) and in a melt water lens (4–5 ppt), while extracellular DMSP concentrations were as high as 149 and 54 nM, respectively in these habitats. DMS in a melt water lens was relatively high at 11 nM. During the ice-free summer in the coastal Davis area, DMS concentrations in surface seawater were highest immediately following breakout of the fast ice cover in late December (range 5–14 nM), and then remained at relatively low concentrations through to late February (< 0.3–6 nM). These measurements support the view that the melting of Antarctic sea ice produces elevated seawater DMS due to release of sea ice DMS and DMSP.     

A modified analytical method for the shipboard determination of nanomolar concentrations of orthophosphate in seawater

A method for the determination of nanomolar concentrations of orthophosphate in oligotrophic seawater developed by Liang et al. (2007) has been modified to make it fully feasible for shipboard application and for faster sample throughput with minimized sample volume. The technique is based on the flow injection method with solid phase extraction on a Sep-Pak C18 cartridge and colorimetric detector. The Schlieren effect was minimized by rinsing the cartridge sequentially with 5 mL water and 2 mL 95% ethanol solution. With three micro pumps in parallel, savings of up to 80% in amount of reagents and 25% volume of seawater samples could be achieved in comparison to the previous method. Variation of stopped flow time and sample loading time gave 3 different standard curves, which corresponded to 3 linear ranges within 3.4 and 515 nM. The modified method permits the analysis of samples over a wide range of concentrations, and has been successfully applied to shipboard determination of trace orthophosphate in more than 200 seawater samples during a one-month cruise in the South China Sea. For seawater at concentrations of 20.6, 82.5, 206.2 nM orthophosphate, the relative standard deviations (RSD) (n = 6), determined daily for 6 days on board ship were 4.45%, 4.73% and 6.75%, respectively. Five seawater samples collected in the Station SEATS (South East Asia Time Series Station at 18°N, 116°E) were analyzed using the present method both on board and in a land-based laboratory, as well as with the magnesium hydroxide-induced coprecipitation (MAGIC) method, and showed no significant difference according to the statistical t-test.     

Sources and sinks of low molecular weight organic carbonyl compounds in seawater

Results from laboratory studies indicated that low molecular weight (LMW) carbonyl compounds, especially formaldehyde, acetaldehyde, acetone and glyoxal, can be formed in seawater by photochemical processes. Once formed, these compounds appear to be readily consumed by biota. These results suggest that concentrations of LMW carbonyl compounds should undergo diurnal variations in the illuminated layer of the sea. In support of this, diurnal fluctuations of LMW carbonyl concentrations were observed in humic-rich surface waters off the west coast of Florida over a three day sampling period using a shipboard HPLC system. Fluctuations in acetaldehyde were particularly strong and reproducible, with steady night-time concentrations of 2–3 nM and day-time concentrations reaching a maximum of 20–30 nM in the early afternoon. In contrast, diurnal fluctuations in formaldehyde were less distinct, ranging from 15 to 50 nM.The laboratory and field results are discussed in terms of biotic/abiotic sources and sinks of LMW carbonyl compounds in surface seawater. It is speculated that photooxidative cleavage of biologically refractory dissolved organic matter (DOM) in seawater to yield LMW organic fragments, such as carbonyl compounds, may be important in the breakdown and geochemical cycling of DOM in the ocean.     

Photochemical formation of glyoxylic and pyruvic acids in seawater

Glyoxylic and pyruvic acids were formed when filter-sterilized seawater was exposed to solar radiation. Production rates varied from samples collected from distinctly different regions of the sea. Humic-rich seawater from the Florida Bay exhibited net photochemical production rates (glyoxylate, 27.5 nM/W-h m⁻²; pyruvate, 12.9 nM/W-h m⁻²) that were significantly greater than net production rates for humic-poor water (glyoxylate, 3.1 nM/W-h m⁻²; pyruvate, 1.8 nM/W-h m⁻²) collected in the Gulf Stream. When seawater was not filtered, the concentrations of glyoxylate and pyruvate were found to undergo diurnal variations resulting from an imbalance between biological and photochemical processes.A depth profile of the glyoxylate concentration from several oceanic stations showed a pronounced daytime maximum in the upper 10 m; this finding is consistent with laboratory results that demonstrated that glyoxylate is formed photochemically in seawater. Pyruvate, in contrast, showed no clear trend with depth; its distribution in the water column may be primarily controlled by biological processes rather than by photochemical processes.Biological processes are generally thought to control the spatial and temporal distribution of simple organic metabolites in seawater. Our results show that photochemical processes may also be important in the marine cycling of some biochemical compounds.     

The behaviour of a Cu(II) ion selective electrode in seawater; copper consumption capacity and copper determinations

Determinations of copper consumption capacity (CuCs.C) and labile copper concentrations in surface coastal seawater, using a copper ion selective electrode (Cu-ISE) potentiometric method under predominantly diffusive conditions, are reported. For evaluation of the copper concentrations, the points of the endpoint contiguity zone of the CuCs.C titration curve were treated by an ISE multiple standard addition technique. The results were compared with those obtained by means of a Chelex-100 (calcic form) ‘batch’ procedure-potentiometric stripping analysis.The labile copper of the sample was determined at concentrations down to 10.70 nM with an average RSD of 12%, independent of the Cu-ISE employed. For adjacent subsamples, the mean CuCs.C values obtained for El Way seawater were equivalent to 81.05 and 48.00 nM copper, with an RSD of 4 and 7%, and for Isla Santa Maria seawater the value was equivalent to 70.27 nM copper, with an RSD of 7%. The theoretical approach of the electrode diffusive mechanism proposed, which would depend, fundamentally, on the adsorptive, complexing and reducing properties of the dissolved organic matter in the seawater sample, allows simultaneous analytical determination of CuCs.C and labile copper concentration in seawater.     

Large temporal changes in contributions of groundwater-borne nutrients to coastal waters off a volcanic island

We examined the contribution of submarine groundwater discharge (SGD) to nutrient budgets in Hwasun Bay, Jeju Island, Korea in August 2009, October 2014, and May 2015. The concentrations of dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorus (DIP) in fresh groundwater were in the range of 285?716 μM and 2.3?3.2 μM, respectively, which were each 1?2 orders of magnitude higher than those in the bay seawater. The outer-bay seawater flowing into the bay was oligotrophic (2.9 ± 1.9 μM for DIN and 0.2 ± 0.3 μM for DIP). Nutrient budget calculations were performed for each season by accounting for submarine fresh groundwater discharge (SFGD) and water residence times. In August 2009 (DIN = 1.8 μM and DIN:DIP ratio = 4.6 for the outerbay water), DIN inputs from SFGD accounted for approximately 40% of the DIN inventory in the bay seawater. In October 2014 (DIN = 1.1 μM and DIP < 0.05 μM for the outer-bay water), DIP from SFGD accounted for approximately 100% of the DIP inventory in the bay seawater. In May 2015, mean concentrations of DIN and DIP in the bay seawater were 8.6 ± 12 μM and 0.11 ± 0.04 μM, respectively, with conservative behaviors in the bay seawater in association with excessive groundwater inputs. These results imply that SGD plays a critical but different role in nutrient budgets and stoichiometry in coastal waters off a volcanic island depending on open-ocean nutrient conditions.     

A solvent extraction method for the colorimetric determination of nanomolar concentrations of silicic acid in seawater

A solvent extraction method for measuring nanomolar concentrations of silicic acid in seawater is described. The procedure is based on the formation of beta silicomolybdic acid by reaction of silicic and molybdic acids at low pH, extraction of the combined acid into n-butanol and reduction with a mixture of p-methylaminophenol sulfate and sulfite. The concentration of the resulting blue silicomolybdous acid in the extract is determined colorimetrically. The method has 30 times the sensitivity and 14 times the precision of standard aqueous analyses. Molar absorbance is 2.29 × 10⁵ in seawater with a precision of ± 2.5 nM Si for concentrations <- 50 nanomolar. Sensitivity in seawater is 70% of that in deionized distilled water owing to a significant salt effect. Natural concentrations of arsenate, arsenite and germanic acid cause negligible interference; however, phosphate interference is equivalent to 11 ± 1 nM Si over a broad range of phosphate concentrations, resulting in an error of ± 1 nM in the corrected silicic acid concentration measurement.     

Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe_R) in the absence and presence of 2 μM Dp, Fe_R being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H₂O₂ and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe_R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe_R, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe_R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.     

Estimates using fluorescence spectroscopy of the present state of petroleum hydrocarbon contamination in the water column of the northwest Atlantic Ocean

Concentrations of petroleum hydrocarbons in seawater from the general region between Nova Scotia and Bermuda were estimated using fluorescence spectroscopy. Concentrations in surface water (0–3 mm) averaged 20.4 μg/l, and in water from 1 and 5 m they averaged 0.8 and 0.4 μg/l respectively. No significant concentrations could be detected in deeper water. There was considerable variability in the concentrations suggesting that the distribution of oil in seawater is quite patchy, especially in surface waters. Seawater samples for hydrocarbon analysis cannot be collected with conventional sampling equipment. Due to adsorption problems, the inner surface of samplers must come into contact only with the water being sampled and must be rinsed with organic solvent after samples are removed. Because these precautions were not taken in previous investigations, much of the published data of hydrocarbons in seawater is unreliable.     

Organic and inorganic speciation of copper in the Irish Sea

The metal complexing ability of surface water of the Irish Sea has been measured by the MnO₂ adsorption method. In all samples strong copper-chelating compounds are present at concentrations of 60–150 nM, with conditional stability constants (log values) of 10.0–10.4. The concentrations of Cu, Pb and Cd in the samples are 16–39 nM, 1–7 nM and 0.1–2 nM, respectively; much less than the ligand concentrations. The organic compounds form complexes with 94–98% of dissolved copper, and therefore constitute the major form of copper in surface water of the Irish Sea. Recalculation of speciation of the inorganic fraction of copper in seawater reveals that the major complex ion is that of CuCO₃⁰ (60%), followed by CuOH⁺ (16%) and Cu(OH)₂⁰ (16%). Complexes with borate ions form a small and rather insignificant fraction of 1%.     

Dissolved free amino acids in coastal seawater using a modified fluorometric method

The method of Parsonset al. (1984) for measuring dissolved free amino acids (DFAA) in coastal seawater was modified. We found considerable interference in DFAA determination from ammonia dissolved in coastal seawater, although the interference of urea could be ignored. For DFAA analysis for coastal seawater samples, ammonia determinations for the same sample are needed to correct DFAA values. For coastal surface seawater samples from all over the Seto Inland Sea, Japan, values of DFAA ranged from undetectable to 1.87 μg-at N/l when corrected for ammonia, while uncorrected values ranged from undetectable to 2.61 μg-at N/l. DFAA, urea, nitrate+nitrite, ammonia and DON concentrations in surface seawater collected in the Seto Inland Sea were analyzed simultaneously. DFAA at four seasons constituted from 1.4 to 10.1% of DON, with a mean value of 6.5%. The concentration of urea was similar to that of DFAA and often higher than that of ammonium, although generally lower than that of nitrate.     

Simultaneous Measurement of Hydrogen Peroxide and Fe Species (Fe(II) and Fe<Subscript>(tot)</Subscript>) in Okinawa Island Seawater: Impacts of Red Soil Pollution

The northern part of Okinawa Island suffers from red soil pollution—runoff of red soil into coastal seawater—which damages coastal ecosystems and scenery. To elucidate the impacts of red soil pollution on the oxidizing power of seawater, hydrogen peroxide (HOOH) and iron species including Fe(II) and total iron (Fe_(tot), defined as the sum of Fe(II) and Fe(III)) were measured simultaneously in seawater from Taira Bay (red-soil-polluted sea) and Sesoko Island (unpolluted sea), off the northern part of Okinawa Island, Japan. We performed simultaneous measurements of HOOH and Fe(II) because the reaction between HOOH and Fe(II) forms hydroxyl radical (•OH), the most potent environmental oxidant. Gas-phase HOOH concentrations were also measured to better understand the sources of HOOH in seawater. Both HOOH and Fe(II) in seawater showed a clear diurnal variation, i.e. higher in the daytime and lower at night, while Fe_(tot) concentrations were relatively constant throughout the sampling period. Fe(II) and Fe_(tot) concentrations were approximately 58% and 19% higher in red-soil-polluted seawater than in unpolluted seawater. Gas-phase HOOH and seawater HOOH concentrations were comparable at both sampling sites, ranging from 1.4 to 5.4 ppbv in air and 30 to 160 nM in seawater. Since Fe(II) concentrations were higher in red-soil-polluted seawater while concentrations of HOOH were similar, •OH would form faster in red-soil-polluted seawater than in unpolluted seawater. Since the major scavenger of •OH, Br⁻, is expected to have similar concentrations at both sites, red-soil-polluted seawater is expected to have higher steady-state •OH concentrations.     

Methyl halide production and loss rates in sea water from field incubation experiments

Experiments were conducted in the field to determine the non-chemical loss rate of methyl iodide in seawater and to examine production rates of methyl halides. The loss rate of added C13 labelled methyl iodide, present at concentrations similar to those found in seawater, corrected for chemical loss due to reaction with Cl⁻ varied from < 1 to 18% day^− 1, with a mean value of 7%. This rate of loss is much lower than that which was proposed by Bell et al. [Bell, N., Hsu, L., Jacob, D. J., Schultz, M. G., Blake, D. R., Butler, J. H., King, D. B., Lobert, J. M., Maier-Reimer, E., 2002. Methyl iodide: Atmospheric budget and use as a tracer of marine convection in global models, Journal of Geophysical Research-Atmospheres 107(D17), 4340-4351.] to account for the large discrepancies between observed and predicted mid-latitude concentrations of CH₃I based on their global photochemical source model. The suitability of several types of container for seawater incubations was studied and only quartz tubes appeared to be free of experimental artifact. Collapsible polyvinyl fluoride containers showed major production of methyl halides on irradiation with simulated sunlight. Polyethylene containers caused spurious production of methyl iodide at lower rates.     

Distribution of Trace Bioelements in the Subarctic North Pacific Ocean and the Bering Sea (the R/V Hakuho Maru Cruise KH-97-2)

A column concentration-high resolution inductively coupled plasma mass spectrometry (ICP-MS) determination was applied to measure the total dissolved concentrations of Fe, Co, Ni, Cu and Zn in seawater collected from the subarctic North Pacific (~45°N) and the Bering Sea in July–September 1997. Total adsorbable Mn was determined on board by column electrolysis preconcentration and chemiluminescence detection. The vertical profiles for Fe, Ni and Zn were nutrient-like. The deep water concentration of Fe was ~0.5 nM in the northeast Pacific (18°-140°W) and increased to ~1 nM in the northwest Pacific (161°E) and ~2 nM in the Bering Sea (57°N, 180°E). The deep water concentrations for Ni and Zn in the Bering Sea were also 1.3–2 times higher than in the North Pacific. The profiles for Co and Cu were examined in the subarctic North Pacific, and results obtained were consistent with previous reports. There was a significant correlation between the concentrations of Co and Mn except for surface mixed layer. The profiles for total adsorbable Mn were similar to the reported profiles for total dissolvable Mn. The deep water concentration of Mn in the Bering Sea was also 4 times higher than in the North Pacific. Iron and zinc were depleted in surface water of the subarctic North Pacific. The relationship between these trace elements and nutrients suggests that these elements could be a limiting factor of phytoplankton productivity. In the Bering Sea, surface water contained ~0.3 nM of Fe. The Zn concentration, which was less than the detection limit in surface water, increased at shallower depths (~30 m) compared with the subarctic North Pacific. These results imply a higher flux of Fe and Zn to surface water in the Bering Sea. This in turn may cause the ecosystem in the Bering Sea characterized by a dominance of diatoms and high regenerated production.     

Calibration of a chalcogenide glass membrane ion-selective electrode for the determination of free Fe in seawater: I. Measurements in UV photooxidised seawater

Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe_2.5(Ge₂₈Sb₁₂Se₆₀)_97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe³⁺ concentrations ranging from 10⁻¹⁰ M to less than 10⁻²⁵ M Fe³⁺. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10⁻⁵ M Fe³⁺, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe³⁺] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10⁻⁵ M Fe³⁺ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10⁻² nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe³⁺ at concentrations typically found in natural seawater.     

Chemical fractionation of zinc versus cadmium among other metals nickel, copper and lead in the northern North Sea

Concentrations of dissolved Ni, Cu, Zn, Cd and Pb were measured in water samples collected during a cruise with R.V Pelagia (29-6/14-7-1993) in the northern North Sea and N.E. Atlantic Ocean. At least six depths (0–90 m) were sampled with modified Go-Flo samplers from a rubber zodiac. In the study area, the first 25 m were well mixed and stratification occurred below this depth. The local bloom of Emiliania huxleyi hardly affected the trace metals concentration, except for some removal of Cd as seen from its correlation with nitrate. The mean dissolved concentrations were for Ni (3.66 nM), Cu (1.61 nM), Zn (4.5 nM), Cd (48 pM) and Pb (108 pM). These concentrations are among the lowest reported for the North Sea and are of similar magnitude to those found in the eastern North Atlantic at the same latitude. Zn was the only exception with values 10 times higher compared to those in the Atlantic Ocean, suggesting external inputs, mainly atmospheric and possibly from surrounding land masses. The observed ratio Zn:Cd in the North Sea and estuaries is in between the high ratio 600–900 for continental sources and the low ratio 5–10 for oceanic waters. Latter low ratio is consistent with the 21-fold stronger inorganic complexation of Cd in seawater which, in combination with the preferential biological uptake of Zn, may lead to the observed about hundredfold fractionation of Zn versus Cd in the marine system. Other processes may play a role but would need further investigation. The dissolved Pb values tend to be lower than found before in the North Sea, indicating decreasing inventories due to reduced anthropogenic emissions.     

北黄海二甲基硫(DMS)的海-气释放及其对气溶胶中非海盐硫酸盐的贡献

根据2006年7～8月和2007年1月对北黄海进行的大面调查,分析研究了夏冬季表层海水中二甲基硫(DMS)的浓度分布和海-气交换通量.研究表明:表层海水以及大气中DMS浓度季节变化明显,夏季平均值分别是冬季的3.2和3.7倍.相关性分析显示,海水中DMS和Chl a浓度存在明显的相关性,说明浮游植物生物量是影响DMS浓度分布的1个重要因素.利用Liss和Merlivat公式(LM86)估算了北黄海夏冬季DMS的海-气交换通量,其平均值分别为7.31和4.98 μmol·m-2·d-1.另外,根据测定的大气中甲基磺酸盐(MSA)和非海盐硫酸盐(Nss-SO2-4)的浓度及比例,估算出夏冬季北黄海生源硫释放对气溶胶中Nss-SO2-4的贡献比例分别为10.1%和2.8%.此结果表明北黄海大气中Nss-SO2-4主要来源于人为排放.