Surfactants in the sea-surface microlayer and their contribution to atmospheric aerosols around coastal areas of the Malaysian peninsula

A study was done to determine the concentrations of surfactants on the sea-surface microlayer and in atmospheric aerosols in several coastal areas around the Malaysian peninsula. The concentrations of surfactants from the sea-surface microlayer (collected using rotation drum) and from aerosols (collected using HVS) were analyzed as methylene blue active substances and disulphine blue active substances through the colorimetric method using a UV-vis spectrophotometer. The results of this study showed that the average concentrations of surfactants in the sea-surface microlayer ranged between undetected and 0.36 ± 0.34 μmol L⁻¹ for MBAS and between 0.11 ± 0.02 and 0.21 ± 0.13 μmol L⁻¹ for DBAS. The contribution of surfactants from the sea-surface microlayer to the composition of surfactants in atmospheric aerosols appears to be very minimal and more dominant in fine mode aerosols.     

A review of pollutants in the sea-surface microlayer (SML): a unique habitat for marine organisms

Boundary layers between different environmental compartments represent critical interfaces for biological, chemical and physical processes. The sea-surface microlayer (uppermost 1-1000 microm layer) forms the boundary layer interface between the atmosphere and ocean. Environmental processes are controlled by the SML, and it is known to play a key role in the global distribution of anthropogenic pollutants. Due to its unique chemical composition, the upper organic film of the SML represents both a sink and a source for a range of pollutants including chlorinated hydrocarbons, organotin compounds, petroleum hydrocarbons, polycyclic aromatic hydrocarbons (PAH) and heavy metals. These pollutants can be enriched in the SML by up to 500 times relative to concentrations occurring in the underlying bulk water column. The SML is also a unique ecosystem, serving as an important habitat for fish eggs and larvae. Concentration ranges and enrichment factors of pollutants in the SML in different areas of the world's oceans have been critically reviewed, together with available toxicity data for marine biota found within the SML. Overall, the SML is highly contaminated in many urban and industrialized areas of the world, resulting in severe ecotoxicological impacts. Such impacts may lead to drastic effects on the marine food web and to fishery recruitment in coastal waters. Studies of the toxicity of fish eggs and larvae exposed to the SML contaminants have shown that the SML in polluted areas leads to significantly higher rates of mortality and abnormality of fish embryos and larvae.     

Distribution and cycling of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) in the sea-surface microlayer of the Yellow Sea, China, in spring

The distributions of dimethylsulfide (DMS) and its precursor, dimethylsulfoniopropionate (DMSP), were examined in the surface microlayer and corresponding subsurface water of the Yellow Sea, China, in April 2006. The average concentrations of DMS and DMSP of dissolved (DMSPd) and particulate (DMSPp) forms were 5.42 (1.78–12.75), 9.22 (2.85–19.73) and 17.50 (4.33–36.09) nmol L⁻¹ in the subsurface water, and those in the surface microlayer were 4.92 (1.69–10.66), 17.08 (3.13–38.82) and 22.54 (4.85–47.24) nmol L⁻¹, respectively. The enrichment factor (EF) of DMS in the microlayer ranged from 0.47 to 2.24 with a mean of 0.98. In contrast, DMSPd and DMSPp appeared to be enriched in the microlayer with average EFs of 1.98 and 1.39, respectively. A close correlation of integrated DMS, DMSPp and chlorophyll a concentrations for compiled data from all stations in the microlayer and the subsurface water indicated that phytoplankton biomass might play an important role in controlling the distributions of biogenic sulfurs in the study area. Moreover, a statistically significant relationship was found between the microlayer concentrations of DMS, DMSP and chlorophyll a and their subsurface water concentrations, suggesting a close linkage between these two water compartments. Interestingly, we observed higher biological production rates and consumption rates of DMS in the microlayer relative to the subsurface water. Furthermore, the DMS production rates were closely correlated both with DMSPd and chlorophyll a concentrations. Our study showed that the major sink of DMS in microlayer was escape into the atmosphere, which greatly exceeded its bacterial consumption. A preliminary estimate for average flux of DMS from the Yellow Sea to the atmosphere was 6.41 μmol m⁻² d⁻¹ during spring.     

广州麓湖大气多环芳烃的干湿沉降

以广州麓湖为小型城市湖泊的代表,对大气中多环芳烃的颗粒态沉降进行了连续一年的采样与分析. 结果表明,年均颗粒态多环芳烃的沉降通量为0.47mg/( m2·a). 全年直接由大气输入到麓湖的颗粒态多环芳烃总量约为0.1kg. 不同季节相比,夏季多环芳烃的沉降通量略高于秋季,而冬春季最高. 对比大气总悬浮颗粒物中多环芳烃的组成发现,当降雨量增大时,沉降颗粒物中多环芳烃的组成逐渐趋近于大气总悬浮物中多环芳烃的组成. 广州地区雨热同期、干冷咸至的季风气候特点,以及由此导致的大气颗粒物粒径变化和PAHs的气-粒分配变化,与大气PAHs污染程度一起,共同控制着沉降颗粒物中PAHs相对组成的季节变化.     

Occurrence and fate of polycyclic aromatic hydrocarbons in the coastal surface microlayer

Polycyclic aromatic hydrocarbons (PAHs) were measured in the coastal sea surface microlayer (SML), the sub-surface waters (SSW) and the overlying atmosphere in order to investigate the influence of the SML on contaminant enrichment and air-sea exchange. Samples were collected at two contrasting locations of the NW Mediterranean, one urban influenced (off Barcelona, Spain) and another comparatively clean (off Banyuls-sur-Mer, France). Statistical data analysis confirmed the accumulation of PAHs in the SML with respect to the SSW (20.3+/-9.1 vs. 13.1+/-10.0 ng L(-1) in the dissolved phase; 709+/-207 vs. 158+/-111 ng g(-1) in the particulate phase). This accumulation was higher at the contaminated location (Barcelona station) compared with the more pristine one, with PAH enrichments 1.5 and 4.5 times higher for the dissolved and particulate phases, respectively, indicating that the enrichment of PAHs in the SML is dominated by particle transport processes.     

PCBs and PAHs in sea-surface microlayer and sub-surface water samples of the Venice Lagoon (Italy)

Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) are two classes of micropollutants intensively monitored and regulated due to their toxicity, persistency and wide diffusion. Their concentrations have been investigated in sea-microlayer (SML) and sub-surface water (SSW) samples collected at two sites of the Venice Lagoon, a fragile ecosystem highly influenced by industrial and anthropogenic emissions. The total sigmaPCB concentration varies from 0.45 ng/l to 2.1 ng/l in SSW while a clear enrichment is observed in the SML, where it ranges from 1.2 ng/l to 10.5 ng/l. The total sigmaPAH concentration shows marked differences between the two stations and varies from 12.4 ng/l to 266.8 ng/l in SSW; in SML it is more uniform and ranges from 19.6 ng/l to 178.9 ng/l. The enrichment factors are not larger than 1 for both pollutants in the 'dissolved' phase, while they are most significant for the 'particulate' phase (sigmaPCB: 5-9; sigmaPAH: 4-14).     

Atmospheric deposition to watersheds in complex terrain

Single collection stations for wet or bulk deposition are generally inadequate to describe atmospheric inputs to watersheds in complex terrain. Atmospheric deposition is delivered by wet, dry and cloud deposition processes, and these processes are controlled by a wide range of landscape features, including canopy type and structure, topographic exposure, elevation and slope orientation. As a result, there can be a very high degree of spatial variability within a watershed, and a single sampling point, especially at low elevation, is unlikely to be representative. Atmospheric inputs at the watershed scale can be calculated from the whole watershed mass balance if the outputs and within-watershed sources and sinks are known with sufficient accuracy. Alternatively, indices of atmospheric deposition such as Pb accumulation in the forest floor and SO²⁻₄ flux in throughfall can be used to characterize patterns of total deposition, and these indices can be used to model deposition to the entire watershed based on known landscape features such as elevation and canopy type. © 1997 John Wiley & Sons, Ltd.     

Atmospheric wet and dry deposition of dissolved inorganic nitrogen to the South China Sea

At the global scale,atmospheric inputs of nitrogen are an important source of the new nitrogen that supports new marine production,especially in oligotrophic open oceans and marginal seas.This study reports quantities of atmospheric deposition of dissolved inorganic nitrogen(DIN) to the largest marginal sea in the North Pacific(the oligotrophic South China Sea,SCS) based primarily on rainwater sampling in the open northwestern region(Yongxing Island) from 2013 to 2015,and aerosol sampling from the SCS basin in June 2017.Atmospheric wet and dry deposition of DIN and their potential contributions to productivity were estimated.The volume-weighted mean rainwater concentrations during the wet and dry seasons were 4.9 and 18.1 μmol L~(-1) for N+N(NO_3~-+NO_2~-),and 5.7 and 4.0μmol L~(-1) for NH_4~+,respectively.Rainwater concentrations of DIN were lower in the marginal seas than in the open ocean.The aerosol NO_3~-concentration was 1.15±1.18 μg m~(-3) during the wet season,which is slightly lower than reported for the East China Sea and East Sea,but higher than in the Arabian Sea.Monthly wet and dry deposition rates ranged from 0.4-3.9 and 0.4-1.2 mmol m~(-2) mon~(-1) for NO_3~-,and 0.2-1.3 and 0.01-0.02 mmol m~(-2) mon~(-1) for NH_4~+,respectively.The annual wet and dry deposition fluxes of DIN were estimated to be 16.8 and 10.1 mmol m~(-2)yr~(-1),respectively.Compared to other marginal seas,the SCS receives less atmospheric NO_3~-inputs than the Yellow Sea,East China Sea,East Sea,and northeastern Mediterranean Sea.The total atmospheric DIN deposition may account for 1.8-11.1% of the nitrogen supporting new production and 0.7-1.8% of the nitrogen supporting primary production.     

Atmospheric chloride deposition in continental Spain

The atmospheric bulk deposition rate of chloride in continental Spain was studied to get basic information in order to help in the evaluation of diffuse recharge to aquifers through an environmental chemical balance. Both new, recent data and bibliographic data have been used. Most sampling records are less than 5 years long and often only 1 year long. This means that the calculated mean yearly bulk deposition rate of chloride is quite uncertain by 30% on average, and larger than the values derived form records up to 15 years long. A map of atmospheric bulk deposition of chloride has been drawn using ordinary kriging. The mean bulk deposition rate of chloride varies from 1 to 30 g m^?2 year^?1 in coastal areas, with strong negative landward gradients between 0·1 and 1 g m^?2 year^?1 km^?1. In the centre of the Iberian Peninsula, chloride deposition rates vary from 0·2 to 0·5 g m^?2 year^?1, with gradients around or less than 5 × 10^?3 g m^?2 year^?1 km^?1. The coefficient of variation of the mean bulk atmospheric deposition rate of chloride, for any place, ranges from 0·1 to 1. Values larger than ～0·5 are not a good indicator of natural uncertainty for this series of data that has a skewed distribution. The map of bulk deposition rate and its error is one of the terms needed for aquifer recharge estimation by means of the chloride ion balance. Copyright © 2008 John Wiley & Sons, Ltd.     

Chlorinated pesticides and PCBs in the sea-surface microlayer and seawater samples of Singapore

Sea-surface microlayer (SML) and seawater samples collected from Singapore's coastal marine environment were analyzed for selected chlorinated pesticides and polychlorinated biphenyls (PCBs). The SML is a potential site of enrichment of persistent organic pollutants (POPs) compared to the underlying water column. The concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB in subsurface (1 m depth) seawater were 0.4-27.2 ng/l (mean 4.0 ng/l), 0.01-0.6 ng/l (mean 0.1 ng/l) and 0.05-1.8 ng/l (mean 0.5 ng/l) respectively. In the SML, the concentration ranges of SigmaHCH, SigmaDDT and SigmaPCB were 0.6-64.6 ng/l (mean 9.9 ng/l), 0.01-0.7 ng/l (mean 0.2 ng/l) and 0.07-12.4 ng/l (mean 1.3 ng/l) respectively. High spatial and temporal distribution was observed for all POPs measured. However, overall levels measured in the SML were lower than levels reported in the literature for SML samples from temperate coastal regions-possibly due to loss of semi-volatile compounds in the tropical climate of Singapore. Atmospheric wet deposition during the monsoon season may be an important source of POPs to the SML. This study provides the first scientific data on POP concentrations and enrichment factors in the SML for Southeast Asia.     

云南阳宗海大气氮、磷沉降特征

大气氮、磷沉降是湖泊水体氮、磷入湖的重要途径之一.为了解阳宗海氮、磷沉降对湖泊富营养化的潜在影响,于2012年5月-2014年4月通过监测阳宗海大气氮、磷沉降,估算氮、磷的大气沉降通量,揭示阳宗海大气氮、磷沉降随时间变化的特征,分析其来源、影响因素等.由于阳宗海是磷限制湖泊,本研究在估算大气氮、磷沉降通量的基础上,特别比较了大气磷沉降入湖量与非点源磷的入湖量,以此评估大气沉降输入磷对湖泊富营养化的潜在影响.研究结果表明:阳宗海总氮年平均沉降通量为248 mg/m~2,春、夏、秋和冬季平均分别为200、306、274和214 mg/m~2,其中夏季沉降通量最大,原因与降雨量增加有关;总磷年平均沉降通量为24 mg/m~2,春、夏、秋和冬季平均分别为18、31、19和27 mg/m~2.大气磷沉降与输入阳宗海的总磷量相比很小,对阳宗海富营养化影响较小.     

Atmospheric nitrogen deposition to the North Sea

The groups of nitrogen components that contribute most to the eutrophication of the sea are ammonia, nitrogen oxides and their respective reaction products. The emission of ammonia is mainly from animal husbandry, whereas the emission of nitrogen oxides is mainly from combustion processes. Ammonia reacts in the atmosphere to form particulate ammonium. Nitrogen oxides react to form nitric acid, nitrous acid, particulate nitrate and peroxyacetyl nitrate. The various nitrogen components have different physical and chemical properties. Therefore, their dry and wet deposition velocities differ. The dry deposition velocity of gas to the sea depends on its solubility, reactivity, concentration in seawater and the wind speed. The dry deposition velocity of a particle depends on its size and the wind speed. The wet removal rate is a function of meteorological conditions. For a gas it further depends on the solubility and reactivity of the gas. For a particle, it further depends on the particle's ability to act as a condensation nucleus for particles. The total deposition of ammonia and its reaction products to the North Sea is about 140 kt N a⁻¹. The total deposition of nitrogen oxides and their reaction products is about 200 kt N a⁻¹.     

乌梁素海大气重金属沉降入湖通量初步估算

重金属元素以大气颗粒物为载体,最终以沉降的方式进入湖泊水体,会引起湖泊的重金属污染.为调查大气沉降对乌梁素海重金属污染的贡献,于2013年7月1日至30日围绕乌梁素海进行大气沉降样品采集,分别测定Cu、Zn、Pb、Cd、Cr、Hg、As 7种重金属元素的含量,并在此基础上估算7月大气重金属沉降通量及入湖量.结果表明,乌梁素海重金属元素大气沉降通量大小依次为:ZnPbCuCrAsHgCd.结合社会调查情况及数据分析显示,大气微粒携带重金属借助风力迁移,较大的沉降通量出现在主风向的下风向区域,说明风向是影响乌梁素海大气重金属沉降通量的主要因素之一.排干输入与大气沉降方式下的乌梁素海重金属入湖量比较发现,大气沉降是除排干输入外湖泊的另一重要重金属污染源.Zn、Pb、Cu、Cr、As、Hg、Cd等重金属元素月入湖量分别为10.6、1.04、1.02、0.833、0.342、0.00514、0.00281t/月.通过估算底泥重金属增量来评价大气沉降对湖泊重金属的贡献表明,大气Hg、Zn、Pb、Cu、As、Cd、Cr等重金属沉降对湖泊贡献率分别为46.4%、44.7%、14.1%、12.0%、8.48%、4.75%、4.03%.     

Interaction of Humic Substances and Polycyclic Aromatic Hydrocarbons (PAHs) during the Biodegradation of PAHs

The influence of humic substances (HS) on the biodegradation of naphthalene, phenanthrene, and pyrene was studied. As a source of HS, water samples of a bog lake (Hohlohsee) were used. PAH degradation experiments, both in the presence and absence of HS were carried out. All investigated PAHs were degradable by the used bacterial mixed culture. A correlation between the number of aromatic rings of the PAHs and the influence of HS on biodegradation has been shown. Adding of HS led to a decrease in degradation rate in the case of naphthalene. By way of contrast, the presence of HS gave rise to an increase of degradation rate in the case of phenanthrene. The degradation processes of pyrene revealed a marked alteration in the presence of HS which could be deduced from the biochemical oxygen demand (t(1/2BOD_max) values). With regard to the total turnover of the PAHs, there was no noticeable difference between degradation experiments with and without HS. Analyses of the HS after degradation experiments using liquid chromatography coupled with DOC detection (LC/OCD) verify that there was no formation of stable associations between HS and PAHs or their metabolites. The determination of the toxicity of the degradation media as luminescence inhibition against Vibrio fischeri (Photobacterium phosphoreum) showed no detoxification as a result of the presence of HS.     

Distribution of dissolved free amino acids, dissolved inorganic nitrogen and chlorophyll a in the surface microlayer and subsurface water of the Yellow Sea, China

Concentrations of 14 different dissolved free amino acids (DFAA), dissolved inorganic nitrogen (DIN), and chlorophyll a were determined in the surface microlayer and subsurface waters at 41 stations in the Yellow Sea, China in April 2006. The concentrations of DFAA in the subsurface water ranged from 0.13 to 1.62 μM, with an average of 0.57±0.05 μM, while those in the surface microlayer varied between 0.22 and 2.6 μM, with an average of 0.94±0.08 μM. Major constituents of DFAA present in the study area were glycine, alanine, glutamic acid, serine and histidine. One-way analysis of variance (ANOVA) showed no significant difference in average mol fractions of DFAA between microlayer and subsurface water (F=0.0440, P=0.8355). Hierarchical cluster analysis of the station similarity based on the DFAA composition in both the surface microlayer and subsurface water separated three clusters of stations at the 70% Bray–Curtis similarity level. The average concentrations of chlorophyll a and DIN were 1.18 (0.34–4.44) μg L⁻¹ and 16.57 (3.98–49.59) μM in the subsurface water, and those in the surface microlayer were 1.30 (0.24–3.97) μg L⁻¹ and 18.56 (5.77–48.93) μM, respectively. Our results showed that concentrations of chlorophyll a (r²=0.7940, n=41, p<0.0001), DIN (r²=0.6939, n=41, p<0.0001) and DFAA (r²=0.2416, n=41, P=0.0011) in the microlayer were, respectively, correlated with their subsurface water concentrations, implying that there was a strong exchange effect between the microlayer and subsurface water. The enrichment factor of DFAA in the microlayer ranged from 0.47 to 2.24 with a mean of 1.88±0.16.     

Distribution of organochlorines in the dissolved and suspended phase of the sea-surface microlayer and seawater in Hong Kong, China

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were measured in the dissolved and suspended particulate phase in the sea-surface microlayer (SML) and subsurface water (SSW) collected from Hong Kong's coastal environment. The concentration ranges (pg/L) for summation sigmaHCHs, summation sigmaDDTs and summation sigmaPCBs in the SSW dissolved phase (DP i.e. sum of truly dissolved and colloidal phase) were 409-940 (mean 602), 774-5583 (mean 1908) and 266-433 (mean 278), respectively. The concentration ranges (pg/L) for summation sigmaHCHs, summation sigmaDDTs and summation sigmaPCBs in SSW suspended particulate matter (SPM) were <5-85 (mean 59), 358-1369 (mean 787) and 85.6-273 (mean 172), respectively. The enrichment factor of PCBs and OCPs in the SML varied between 1.1 and 4.5 for the DP, and 0.4-8.2 for the SPM. The distribution of contaminants between DP and SPM in both the SML and SSW indicates that particulate matter plays an important role in the distribution and fate of DDTs and PCBs, but not for HCH isomers. The Pearl River Estuary is likely to be a major source of contaminants transported to Hong Kong.     

京蒙沙源区水库大气磷干、湿沉降污染特征

为阐明典型沙源区水库大气磷干、湿沉降的污染特征及其对水域磷素污染的贡献,为水库富营养化治理提供科学依据,以京蒙沙源区大河口水库库区为研究区,于2014年沿水库岸边布设12个大气沉降监测站点,采集干、湿沉降样品,测定干、湿沉降中总磷(TP)浓度,计算全年各月大气TP干、湿沉降通量和年入库TP污染负荷量.结果表明:研究区大气干、湿沉降季节差异显著,全年各月TP干沉降通量变化范围为4.89~35.76 kg/(km~2·月),主要集中在春季4月和秋季10月.最大TP干沉降通量出现在春季风沙最为严重的4月;湿沉降主要集中在夏季(6—8月),最大TP湿沉降通量出现在降雨量最大的8月,为28.88 kg/(km~2·月),且TP湿沉降通量与降雨量呈显著正相关.2014年大气TP沉降入库污染负荷量为0.719 t,占同期滦河和吐力根河两条河流入库TP污染负荷比率为51.17%,成为影响和限制大河口水库磷营养盐水平的重要源项之一.     

Enrichment and partitioning of polycyclic aromatic hydrocarbons in the sea surface microlayer and subsurface water along the coast of Xiamen Island,China

Sea microlayer (SML) and subsurface water (SSW) samples were collected around Xiamen Island to study the enrichment and partitioning of polycyclic aromatic hydrocarbons (PAHs). Total PAH concentrations ranged from 93.43 to 411.05 ng L⁻¹ in the SML and 49.29–279.42 ng L⁻¹ in the SSW. Compared with the results of previous studies before pollution control measurements, PAHs levels decreased significantly. The enrichment factors (EFs) of dissolved and particulate PAHs varied from 0.68 to 2.71 and 0.43–3.56. EFs showed the consistent enrichment trends with sites and exhibited different enrichment characteristics between 2 and 3 ring PAHs and 4 ring PAHs. Furthermore, the much higher concentrations of BaP (strong carcinogenicity) were accompanied by higher EFs in the SML samples from the Western Xiamen Harbour, which together indicated the risk of impacts to the fish eggs that usually float on the SML water after exposure to oil spills and combustion, contributed directly by the port and shipping activities.     

Nematode response to metal, PAHs and organic enrichment in tourist marinas of the mediterranean sea

The structure of nematode assemblages was investigated in the sediments of two different tourist marinas in the Mediterranean Sea and related to pollution variables. Nematode densities and generic compositions were determined, as were concentrations of heavy metals, PAHs and organic matter. Results showed different assemblages at the two marinas, with a dominance of the genera Paralongicyatholaimus and Daptonema. Significant correlations between nematodes and concentrations of environmental contaminants were found. In particular, Paralongicyatholaimus showed a significant negative correlation with Cu concentrations and was almost absent at the stations where higher Cu concentrations were found. The presence of sensitive/tolerant nematode genera represents a promising tool to identify areas subjected to a higher level of disturbance and to define the correct environmental management strategy for harbors.     

Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05–0.41 and 0.04–4.3 μg l⁻¹ in the SSW, peaking up to 38 and 1366 μg l⁻¹ in the SML, respectively. Dissolved and particulate PAHs ranged 1.9–98 and 1.9–21 ng l⁻¹ in the SSW, amounting up 217 and 1597 ng l⁻¹ in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9–11.5 in the dissolved phase.