The sea-surface microlayer of puget sound: Part II. Concentrations of contaminants and relation to toxicity

Many aquatic contaminants, because of low water solubility (hydrophobicity) or association with floatable particles, concentrate at the sea surface. Thirty-six samples of the sea-surface microlayer (SMIC), the upper 50 μm, were collected from sites in Puget Sound, Washington State. Sites included three urban bays, central Puget Sound, and a rural reference site. Exposure of floating fish eggs to approximately half of these samples resulted in sublethal and lethal toxic effects (Hardy et al., 1987c).Chemical analyses revealed high concentrations of contaminants in many of the samples. Major temporal and spatial differences in sea-surface chemistry occurred, but maximum (for all) and mean (for 1985) concentrations were aromatic hydrocarbons, 8030 (mean 132) μg liter⁻¹: saturate hydrocarbons, 2060 μg liter⁻¹: pesticides, 43·8 (mean 0·46) ng liter⁻¹; PCBs, 3890 (mean 631) ng liter⁻¹; and total metals, 4750 (mean 626) μg liter⁻¹. Stepwise multivariate regression indicated that the percentage of fish eggs developing to normal live larvae decreased with increasing concentrations of a complex mixture of contaminants. Principal component analysis demonstrated that the major types of contaminants did not differ greatly in their statistical contribution to the toxicity, i.e. no single chemical was responsible for the observed toxicity.The chemical composition of the SMIC samples suggested that contamination originated from a variety of sources including atmospheric deposition, terrestrial runoff of fossil fuel combustion products, and sewage disposal.     

Sea-surface microlayer metals enrichments in an urban and rural bay

The sea-surface microlayer is an important interface between the atmosphere and ocean and a collection point for many anthropogenic materials including potentially toxic metals. We developed a glass plate sampler to collect the upper 30 to 55 micrometers of the sea surface. Samples of the microlayer and subsurface bulk water from an urban and rural bay were analysed for concentrations of Pb, Zn, Cu, Cd and Fe. Metal concentrations in both the microlayer and bulk water were generally 2 to 15 times greater in the urban than in the rural bay. Concentrations of metals in the microlayer of both bays averaged 6 to 65 times greater than those in the bulk water. In the urban bay, microlayer concentrations of Pb, Zn and Cu from 10 to > 100 μg 1^?1 were common. Measured microlayer metals concentrations agree well with those predicted from atmospheric deposition rates using a previously derived empirical model developed from laboratory microcosm studies. Further work will be required to determine whether or not these high microlayer metal concentrations contain significant biologically available fractions which could impact fisheries recruitment of larval icthyoneuston.     

Application of the sea urchin sperm bioassay to sewage treatment efficiency and toxicity in marine waters

A newly standardized 60-minute sea urchin (and sand dollar) sperm bioassay was used to measure the toxicity of sewage at each stage in the treatment process. The sensitivity of the sperm bioassay was compared to the results of 48- to 96-hour bioassays with sea urchin and oyster embryos and crab zoeae in side-by-side tests of each sewage type. These data were then used to estimate the dilutions necessary to protect sensitive life stages of marine animals around a proposed sewage outfall in Puget Sound and to select the best bioassay procedure for a post-discharge program for monitoring water column toxicity.Results showed that very little acute toxicity was removed by the primary treatment process but that toxicity was greatly reduced by secondary treatment. A high degree of toxicity was reintroduced by chlorination but this source of toxicity was essentially eliminated by dechlorination. The simple and rapid sperm assay proved more sensitive to all stages of sewage than did the longer embryo and larval assays. Based on the results of the comparative testing and the ease, rapidity and year-round availability of the sea urchin sperm assay (sea urchins in winter, sand dollars in summer), this test was recommended for post-discharge monitoring of sewage effluent-related toxicity in the receiving waters.     

Aquatic surface microlayer contamination in chesapeake bay

The aquatic surface microlayer (SMIC), 50 μm thick, serves as a concentration point for metal and organic contaminants that have low water solubility or are associated with floatable particles. Also, the eggs and larvae of many fish and shellfish species float on, or come in contact with, the water surface throughout their early development. The objectives of this study were (1) to determine the present degree of aquatic surface microlayer pollution at selected sites in Chesapeake Bay, and (2) to provide a preliminary evaluation of sources contributing to any observed contamination.Twelve stations located in urban bays, major rivers, and the north central bay were sampled three times, each at 5-day intervals during May 1986. Samples of 1.4–4.1 each were collected from the upper 30–60-μm water surface (surface microlayer, SMIC) using a Teflon-coated rotating drum microlayer sampler. One sample of subsurface water was collected in the central bay.At all stations, concentrations of metals, alkanes, and aromatic hydrocarbons in the SMIC were high compared with one bulk-water sample and with typical concentrations in water of Chesapeake Bay and elsewhere. SMIC contamination varied greatly among the three sampling times, but high mean contaminant levels (total polycyclic aromatic hydrocarbons, 1.9–6.2 μg 1⁻¹; Pb, 4.9–24 μg 1⁻¹; Cu, 4–16 μg 1⁻¹; and Zn, 34–59 μg 1⁻¹) were found at the upper Potomac and northern bay sites. Three separate areas were identified on the basis of relative concentrations of different aromatic hydrocarbons in SMIC samples - the northern bay, the Potomac River, and the cleaner southern and eastern portions of the sampling area.Suspected sources of surface contamination include gasoline and diesel fuel combustion, coal combustion, and petroleum product releases. Concentrations of metals and hydrocarbons, at approximately half the stations sampled, are sufficient to pose a threat to the reproductive stages of some fish and shellfish. Sampling and analysis of the surface microlayer provides a sensitive tool for source identification and monitoring of potentially harmful aquatic pollution.     

Toxicity of sea-surface microlayer: Effects of hexane extract on baltic herring (Clupea harengus) and atlantic cod (Gadus morhua) embryos

This study was designed to determine whether contaminated sea-surface microlayer was toxic to marine fish embryos in its ntaive form and as a hexane extract. Developing embryos of Atlantic cod (Gadus morhua) and Baltic herring (Clupea harengus) were exposed to hexane extracts of sea-surface microlayer collected from five locations in the North Sea and Baltic Sea. Extracts from two of these locations produced significant embryos mortality as well as severe deformities in live hatched larvae. A control sample of bulk water collected from 20 cm under the surface and extracted in the same way produced no significant mortality or deformities. Significaant changes in timing of hatching were also observed in those samples which produced embryo toxic effects. A comparison of these data with those obtained from code embryos exposed to unextracted microlayer showed a similar biological effect with both unextracted samples and hexane extracts.Chemical analyses revealed the greatest biological effect in samples with petroleum hydrocarbon concentrations between 180 and > 200 μg liter⁻¹. The bulk water control had 1 μg liter⁻¹ while the three samples that showed no biological activity had 3 to 8 μg liter⁻¹ petroleum hydrocarbons. Phthalic acid esters were detected in four samples and chlorinated hydrocarbons in one, but could not be positively correlated with any of the toxic responses. No other chemical contaminants were detected in the five samples.The data presented here show that some sites contain sea-surface microlayer which can be toxic to marine fish embryos: that Baltic herring and Atlantic cod embryos respond similarly to the toxic effects of contaminated microlayer: and that unextracted microlayer and hexane extract of microlayer produce essentially the same toxic effect(s) if only organic contaminants are considered.     

Sea-surface microlayer toxicity off the Florida Keys

A survey of sea-surface microlayer (SSML) toxicity was initiated off the Florida Keys in early 1993. Ex situ toxicity tests, based on the development of the sea urchin, Lytechinus variegatus, demonstrated that 59.2% of SSML samples taken from visibly slicked areas (n=27) were toxic compared to collected subsurface water. A random subset of samples tested a second time using a fish early life-stage test with embryos from the spotted seatrout, Cynoscion nebulosus, confirmed the presence of the toxicant. Results from a partial toxicity identification evaluation (TIE) procedure indicated that an organic compound(s) containing a non-polar functional group was the primary determinant of toxicity in all of the SSML samples tested. While subsequent GC-MS analyses failed to identify a specific compound, they did tend to rule out common xenobiotics, such as organochlorine pesticides as potential toxicants. Preliminary tests, done by an outside laboratory, indicated that two of the most toxic SSML samples contained a brevetoxin, a biotoxin produced by Gymnodinium breve. This is the first report of natural toxins concentrating in the SSML; however, without a completed TIE, including a Phase III—toxicity confirmation procedure, the identification of any toxic agent remains speculative.     

Organic and trace metal contaminants in sediments and English sole tissues from Vancouver Harbour,Canada

As part of a multinational workshop on marine environmental quality, sediments were collected from seven sites in Vancouver Harbour and analyzed for polynuclear aromatic hydrocarbons (PAHs) and organochlorines (OCs), and for trace metals. English sole were collected from five sites, and muscle was analyzed for trace metals and liver for OCs. As expected, sediment PAH and OC concentrations and tissue OC concentrations were higher at sites east of the First Narrows, compared to the outer harbor and reference sites. Sediment PAH concentrations east of the First Narrows were similar to concentrations at moderately contaminated sites in Puget Sound, south of Vancouver Harbour. In contrast, concentrations of OCs in sediments and tissue were low to moderate, even at relatively contaminated sites within Vancouver Harbour. Although several trace metals in sediments were higher than in contaminated sediments from Puget Sound, trace metals measured in fish muscle were lower.     

Toxicity of sea-surface microlayer: Effects on herring and turbot embryos

Marine fish eggs, from herring (Clupea harengus) and turbot (Psetta maxima), were used to test the effects of the sea-surface microlayer on embryonic development. The eggs were exposed in static systems to full strength microlayer and 1,10,50% dilutions. Depending on the sampling site (Helgoland harbour, Kiel Förde, Travemünde marina, Elbe Hamburg Port) and time, microlayer contained varying amounts of Zn, Cd, Cu, Ni, Fe, Pb and Co, in concentrations 100 times above those found in subsurface bulk water. Chlorinated hydrocarbon pesticides were not found at concentrations elevated above bulk water, but considerable amounts of petroleum hydrocarbons and phthalate esters were detected. Microlayer displayed differential concentration-dependent toxicity for each species used in the experiments. Effects on hatching time as well as total hatch (%) and number of abnormal larvae were recorded. Herring eggs were most affected by Helgoland microlayer (suspected effect of high metal content) while turbot eggs were most sensitive to Travemünde and Elbe microlayer (suspected effect of high petroleum hydrocarbons). The usefulness of microlayer studies as a tool for environmental assessment is discussed. An impact of microlayer effects on recruitment in sensitive species is deemed possible.     

大亚湾微表层和次表层海水营养盐的研究

根据1998年秋季（10、11月）、1999年春、秋季（4、5、10月）5个航次对大亚湾海区微、次表层的调查结果，分析了微表层海水对氮、磷、硅营养盐的富集概况，讨论了营养盐与环境因子的关系。结果表明：大亚湾海区微表层海水对氮、磷、硅营养盐均有富集作用，因海况及季节不同，富集因数（EF）与其他海区的有所差别；无论夏季或秋季，大亚湾海区微表层海水中无机氮都以NH4－N为主要存在形态；其余水层则以NO3－N为主要存在形态。结果还表明，微表层、次表层海水中NH4－N与BOD5、COD测值都呈高度显著正相关，与PO4－P和SiO3-Si含量均无相关，说明大亚湾海区水中含氮有机物较含磷有机物丰富。     

Reduction of flatfish habitat as a consequence of the proliferation of an invasive mollusc

Coastal bays provide habitats for juveniles and adults of many marine species. Mont Saint-Michel Bay (MSMB, France) hosts a highly diversified fish community and constitutes one of the most important nursery grounds for many commercially exploited marine species, such as sea bass, flatfish, clupeids and rays in the English Channel. Besides, MSMB also suffers from the massive invasion of an exotic mollusc, the American slipper-limpet (Crepidula fornicata, L.). This species arrived four decades ago and now represents the main filter-feeder biomass in the bay (150 Mt), an order of magnitude larger than local farmed and natural shellfishes. Recent analyses underlined the impact of this small gastropod on the trophic structure of this bay and its negative influence on juvenile sole densities in the nursery grounds. The present study uses a geostatistical approach to explore the effect of the extension of the slipper-limpet on flatfish (common sole Solea solea, L.; plaice Pleuronectes platessa, L.; brill Scophthalmus rhombus, L. and flounder Platichthys flesus, L.) spatial distribution. Data collected during survey of the MSMB at the end of the 1970s and three decades later have been used to build interpolated maps of (1) slipper-limpet and (2) flatfish spatial distributions. Slipper-limpets were concentrated in a small area, in the western part of the MSMB, in the 1970s while today they occupy half of the bay. This rapid proliferation led to the decrease of available surface for flatfishes, which previously occupied the whole bay and are now restricted to its eastern part. The present study highlighted that the negative influence on fish habitat in MSMB is apparently more related to changes in the substratum than to trophic interactions. This invasion has possible consequences on flatfish population renewal at a large scale and may also damage other benthic or demersal species, such as rays.     

Evaluation of the leukoproliferative response of English sole (Pleuronectes vetulus) as a biomarker for immune dysfunction

The leukoproliferative (LP) response of splenic leukocytes from the marine benthic fish, English sole (Pleuronectes vetulus), stimulated with the mitogens lipopolysaccharide (LPS), concanavalin A (Con A), and pokeweed mitogen (PWM) was examined as a biomarker of immunotoxic effects. English sole were exposed to an organic-solvent extract of a sediment contaminated with polycyclic aromatic compounds (PACs) or placed on a reference sediment modified with the PAC contaminated sediment. For both treatments, English sole had an augmented LP response to Con A, no significant change in the response to LPS, and the LP response to PWM showed no consistent relationship to exposure to PACs. In a field study, English sole from a contaminated site had a significantly augmented LP response to Con A and PWM. Fish from a non-urban site also had an augmented LP response to Con A and to LPS relative to fish from another non-urban reference site. Overall, the results demonstrated that although the LP response in splenic leukocytes of English sole to Con A was linked to contaminant exposure, the LP response to Con A did not exhibit high specificity as an indicator of chemical contaminant exposure. However, the concerted use of Con A, LPS, and PWM allowed for identification of apparent chemical-contaminant induced alterations of the LP response in English sole from an urban area of Puget Sound.     

Distribution of silver, mercury, lead, copper and cadmium in central puget sound sediments

Distributions of five of the more toxic heavy metals have been assessed for Puget Sound sediments. Twenty-one Kasten cores were collected for the study. Analysis by Zeeman-corrected graphite-furnace atomic absorption spectroscopy has made possible the accurate and precise determination of silver and cadmium in Puget Sound sediment cores for the first time. Data show that Puget Sound is moderately impacted by anthropogenic Ag, Hg, Pb and Cu. No enrichment of Cd was found. The study also indicates that Puget Sound is quite well mixed with respect to the residence time of particle-bound metals. Toxic metal accumulation sites in the central Sound are determined almost exclusively by grain size, rather than proximity to sources. Estimates are made of trace metal fluxes to the sediments as a function of sediment type and areal distribution.     

Toxicity assessment of sediment cores from Santa Monica Bay,California

During the summer of 1997, sediment core samples were taken at 25 stations in Santa Monica Bay. Toxicity testing was performed on 4-cm sections of the entire length of each core using purple sea urchin fertilization and amphipod survival tests. The sea urchin test identified sections as being toxic at six stations, all located near current or former Hyperion Treatment Plant (HTP) wastewater outfall locations. The amphipod test identified sections from 17 stations as having toxic sediments. The stations having toxic sediments were scattered throughout the bay and toxicity was identified at numerous core depths. Spatial and temporal patterns indicated that toxicity was most strongly associated with the historical disposal of municipal wastewater sludge. Many of the sections toxic to the amphipods did not have chemical levels expected to cause toxicity and were in locations where a source of toxicity was not apparent.     

Influence of sample manipulation on contaminant flux and toxicity at the sediment-water interface

Toxicities of sediments from San Diego and San Francisco Bays were compared in laboratory experiments using sea urchin (Strongylocentrotus purpuratus) embryos exposed to pore water and at the sediment-water interface (SWI). Toxicity was consistently greater to embryos exposed at the SWI to intact (unhomogenized) sediment samples relative to homogenized samples. Measurement of selected trace metals indicated considerably greater fluxes of copper, zinc, and cadmium into overlying waters of intact sediment samples. Inhibition of sea urchin embryo development was generally greater in sediment pore waters relative to SWI exposures. Pore water toxicity may have been due to elevated unionized ammonia concentrations in some samples. The results indicate that invertebrate embryos are amenable to SWI exposures, a more ecologically relevant exposure system, and that sediment homogenization may create artifacts in laboratory toxicity experiments.     

The biogeography and community structure of kelp forest macroinvertebrates

Understanding species distributions and their community structure is increasingly important when taking an ecosystem‐based approach to conservation and management. However, knowledge of the distribution and community structure of species in mid‐range trophic levels (e.g. macroinvertebrates) is lacking in most marine ecosystems. Our study aimed to examine the spatial distribution and community‐level biogeographic patterns of common kelp forest–rocky reef macroinvertebrates in Southern California and to evaluate the effects of environmental gradients on these communities. Quantitative SCUBA surveys were used to estimate macroinvertebrate densities at 92 sites from 2008–2012. Non‐metric multidimensional scaling was used to evaluate spatial patterns of macroinvertebrate communities among Regions. We found that kelp forest–rocky reef macroinvertebrate communities are distinct among different island and mainland regions, and their community patterns exhibited a strong relationship with an environmental gradient (i.e. sea surface temperature) even after controlling for geographic distance between sites. High abundances of urchin species (Strongylocentrotus purpuratus and Strongylocentrotus franciscanus) were strong drivers of regional differences. Macroinvertebrate community patterns were driven by characteristic species that were typically more prevalent at warmer or colder sites. Our results provide the first quantitative analysis of macroinvertebrate community structure within the California kelp forest ecosystem. We also describe the distribution and abundance of 92 conspicuous kelp forest‐rocky reef macroinvertebrates among nine pre‐defined Regions. This study provides important preliminary information on these macroinvertebrate species that will be directly useful to inform management of invertebrate fisheries and spatial protection of marine resources.     

The sea surface microlayer: Biology, chemistry and anthropogenic enrichment

Recent studies increasingly point to the interface between the world's atmosphere and hydrosphere (the sea-surface microlayer) as an important biological habitat and a collection point for anthropogenic materials. Newly developed sampling techniques collect different qualitative and quantitative fractions of the upper sea surface from depths of less than one micron to several centimeters.The microlayer provides a habitat for a biota, including the larvae of many commercial fishery species, which are often highly enriched in density compared to subsurface water only a few cm below. Common enrichments for bacterioneuston, phytoneuston, and zooneuston are 10²−10⁴, 1−10², and 1−10, respectively. The trophic relationships or integrated functioning of these neustonic communities have not been examined.Surface tension forces provide a physically stable microlayer, but one which is subjected to greater environmental and climatic variation than the water column. A number of poorly understood physical processes control the movement and flux of materials within and through the microlayer. The microlayer is generally coated with a natural organic film of lipid and fatty acid material overlying a polysaccharide protein complex.The microlayer serves as both a source and a sink for materials in the atmosphere and the water column. Among these materials are large quantities of anthropogenic substances which frequently occur at concentrations 10²−10⁴ greater than these in the water column. These include plastics, tar lumps, polyaromatic hydrocarbons, chlorrinated hydrocarbons, and potentially toxic metals, such as, lead, copper, zinc, and nickel. How the unique processes occurring in the microlayer affect the fate of anthropogenic substances is not yet clear. Many important questions remain to be examined.     

海水营养状态的灰色关联评价模型及应用

基于计算海水营养状态评价指标的参考序列(u0)和其比较序列(ui)之间的关联度这一思路,建立了一种新的海水营养状态的灰色关联评价模型,并应用这个模型对2001年8月东海区10个主要河口、海湾的水体进行了营养状态评价,结果表明:应用灰色关联海水营养状态评价模型所进行的海水营养状态等级的评价和划分,与实际该区水体的营养状态有很好的吻合。同时,该模型在进行营养状态评价时,能避免人为的主观臆断,并能适应营养状态受PO4-P限制的中国主要近岸河口、海湾等特殊海域的要求,因而可以作为一种科学、实用的海水营养程度评价模型,推广应用于水质评价等研究领域和实际评价中。     

黄渤海沿岸海湾─溺谷型潮汐汊道的地貌结构

本文以丁字湾等基岩海湾为例，论述了黄渤海沿岸海湾－溺谷型潮汐汉道的地貌结构，尤其着重于口门段深槽及涨、落潮三角洲。认为涨、落潮三角洲的发育状况与入湾河流的供沙量、纳潮水域容量、被浪作用、潮差以及口少卜海域的开阔程度有关；泻湖型潮汐汉道的落潮三角洲的典型模式可以应用于海湾－溺谷型潮汐汉道，但涨潮三角洲因受基岩海湾的复杂岸线的限制而不能充分发育。本文还讨论了海湾型潮汐汉道与半开敞海湾在动力和形态中的差异。     

Enhanced extracellular enzymatic peptide hydrolysis in the sea-surface microlayer

The accumulation of dissolved organic matter (DOM) at the air–sea interface is controlled by dynamic physical processes at the boundary between ocean and atmosphere. Much of the DOM concentrated in the surface microlayer is thought to be protein or glycoprotein. Enzymatic hydrolysis of these and other biopolymers is an important step in the microbial uptake of dissolved and particulate organic matter in many aquatic environments. We employed a sensitive fluorescence technique to investigate differences between extracellular enzymatic peptide hydrolysis in the sea surface microlayer and corresponding subsurface water from Stony Brook Harbor, NY. We separated the microlayer from its underlying water and thus measured hydrolysis potential rather than an in-situ process. Peptide turnover was always faster in the microlayer than in subsurface waters. This was confirmed by allowing a new surface film to form on subsurface water; hydrolysis was still faster in the new surface film. In a year-long study, we found the relative difference between turnover times in the surface film and subsurface waters to vary greatly with season. While rate constants of peptide hydrolysis were generally higher in both microlayer and bulk water samples in spring/summer than in fall/winter, the difference in activity between the two environments was greatest in winter. Enhanced hydrolysis in the sea surface microlayer is likely due to the greater concentrations of DOM in the microlayer. Seasonal changes in distribution of hydrolytic activity between surface film and subsurface water probably reflect seasonal variation in the mechanisms of DOM enrichment, which depend on water temperature, substance and energy fluxes across the water–air boundary, activity of aquatic organisms and other seasonal variables.     

北部湾广西沿岸全新世海侵过程的区域差异

通过分析北部湾广西沿岸3个地质钻孔的岩性、地球化学和有孔虫含量特征,确定了其沉积相序,在统一的高程坐标内,对各钻地层中沉积相的高程和年代进行了对比,分析了该区全新世以来海侵过程的区域差异;并以东亚全新世海平面波动曲线作为参照,估算了广西沿岸各主要海湾的构造沉降速度。研究表明:全新世以来,广西沿岸的海侵开始时间并不一致,这是由于各海湾构造沉降运动的区域差异造成的,东部的廉州湾构造基本稳定,而廉州湾以西则经历了较大幅度的构造沉降。构造沉降又导致了海平面波动过程的区域差异,进而影响到了地层形成,如海陆过度相沉积只发育于廉州湾以西遭受海侵时间较晚、相对海平面上升速度较低的区域。