The budget and geochemistry of arsenic in a continental shelf environment

The concentrations of arsenic species in continental-shelf waters of the southeastern U.S. are controlled mainly by simple physical mixing of shelf waters and Gulf Stream intrusions. The biota mediate redox reactions which result in a disequilibrium of arsenic species; up to 20% of the total arsenic (averaging 1.1 μg/l) occurs as unstable arsenite [As (III)] and dimethylarsenic, the remainder consists of thermodynamically favored arsenate [As (V)]. Uptake of arsenic by the biota has a minor effect on arsenic distribution in offshore waters, producing a deep-water arsenate maximum, and minima for arsenite and dimethylarsenic. Riverine and atmospheric arsenic inputs to the shelf waters are relatively insignificant. Southeastern rivers contain only about 0.3 μg/l dissolved arsenic, and the atmosphere adjacent to continental shelf waters contains about 1.7 ng/m³ of As (V), exclusively associated with the particulate fraction.     

The behaviour of dissolved arsenic in the estuary of the River Beaulieu

The chemical forms and distribution of dissolved arsenic species in the estuary of the River Beaulieu (Hampshire, U.K.) are reported. ‘Inorganic arsenic (V)’ in both the marine and riverine estuary inputs are in true solution, passing through ultrafiltration membranes having a nominal molecular weight cut-off of 500 daltons. Extensive removal of dissolved ‘inorganic arsenic (V)’ is apparent from the distribution of arsenic in the estuary, with laboratory mixing experiments indicating that removal is favoured in the low salinity region. ‘Inorganic arsenic (III)’ and methylated arsenic species account for up to 41% and 70% of the dissolved arsenic, respectively, but are only found during the warmer months when water temperatures exceed ca. 12°C.     

黄、东海海域溶解无解机砷分布特征与化学形态

Distribution and chemical speciation of dissolved inorganic arsenic were examined in Yellow Sea and East China Sea. Results demonstrated that: (1) both As(III) and As(V) were detected, with As(V) domin...     

Statistical analysis of estuarine profiles: II application to arsenic in the Tamar estuary (S.W. England)

By combining field observations with a statistical approach and a simple but effective estuarine analogue, the main features of the cycling of arsenic in the Tamar estuary have been elucidated. As(III) and As(V) enrichment in the water column is due to a combination of localized inputs and effective recycling of sediment interstitial waters. The profiles of As(V) are similar to those of NH₄⁺ and are dominated by an estuarine maximum resulting from an input from the sediments. As(III) profiles are correlated with those of dissolved manganese and exhibit both fresh water and estuarine maxima. As(III) appears to be effectively removed at the freshwater/brackish water interface by a combination of heterogenous oxidation, catalysed by hydrous manganese dioxide, and adsorption on to iron oxyhydroxide. The estuarine distribution of As(III) within the water column is consistent with the published rates of oxidation of As(III) to As(V) by both inorganic and microbiological processes. The reduction of As(V) to As(III) in the sediments is incomplete. On the basis of our observations a tentative estuarine arsenic cycle is presented.     

The marine polychaete Arenicola marina: its unusual arsenic compound pattern and its uptake of arsenate from seawater.

Arsenic compounds in the marine polychaete Arenicola marina collected from Odense Fjord, Denmark were determined by HPLC-ICPMS. In contrast to most other marine animals, A. marina contained most of its water soluble arsenic as inorganic forms, arsenite (58%) and arsenate (16%), and arsenobetaine was present as a minor constituent (6%) only. Other arsenic compounds detected in A. marina were dimethylarsinate (4%), two arsenosugars (1 and 3%), tetramethylarsonium ion (1.5%), and arsenocholine (<1%). A new arsenobetaine -trimethylarsoniopropionate-previously only reported in fish, was also present at trace levels (<1%), and an unknown anionic arsenical (approximately 10%) remains unidentified. When A. marina was exposed in laboratory experiments to different concentrations of arsenate in seawater (10, 50. 100, 500 and 1000 microg As 1(-1)) the polychaetes accumulated arsenic in a dose dependent. non-linear manner. Most of the accumulated arsenic was biotransformed to arsenite and dimethylarsinate. with the remainder being accumulated as unchanged arsenate. None of the other arsenic compounds naturally present in A. marina increased in concentration following arsenate exposure.     

Arsenic and antimony species in surface transects and depth profiles across a frontal zone: The Chatham Rise,New Zealand

Measurements of total dissolved arsenic (As(III+V)) and antimony (Sb(III+V) and their simple methylated species are presented for samples collected from three vertical profiles and along three surface transects in the Chatham Rise region, east of New Zealand. As(III+V) concentrations showed a slight increase with depth (16–17 nM at 25 m to 20 nM at 100 m) whereas Sb(III+V) concentrations were conservative with depth (1.02–1.12 nM). Along the three surface water transects, As(III+V) and Sb(III+V) concentrations showed little variation, with average concentrations of 18±2 and 0.99±0.05 nM, respectively. Inorganic arsenic was not correlated with orthophosphate (r²=0.01). Monomethyl- and dimethyl-arsenic (MMAs, DMAs) concentrations (0.04–0.01 and 0.65–0.07 nM, respectively) decreased with depth, suggesting surface water production by biota and degradation at depth. Along the Chatham Rise transect, DMAs concentrations increased on the Rise (0.65 nM maximum) compared to waters north and south of the Rise (∼0.22 nM). Fluctuation in MMAs concentrations were also seen for water samples collected on the Chatham Rise. Monomethyl-, dimethyl- and trimethyl-antimony (MMSb, DMSb, TMSb) species were detected in water samples collected along all the three surface water transects suggesting surface water production by biota. Concentrations of MMSb, DMSb and TMSb in water samples were fairly constant along all the three surface transects (0.06–0.07, 0.015–0.025 and 0.005–0.015 nM, respectively), showing no significant enrichment on the Chatham Rise. These arsenic and antimony results support the current global view that inorganic As and Sb are conservative and the methyl species are of biological origin.     

九龙江口沉积物砷含量的分布特征及与环境因子的相关性

采集九龙江河口表层和柱状沉积物样品,对表层沉积物中总砷、不同形态砷和其他重金属元素、有机质含量以及粒径等参数进行测定.分析了柱状沉积物中总砷和各形态砷的含量,结合沉积速率和响应因子,探讨总砷的污染累计特征.结果表明：（1）沉积物中检出的形态砷是As3＋和As5＋,未检出有机砷.（2）表层沉积物中总砷含量范围为10.03～11.29μg/g,河端总砷含量为11.28μg/g,高于海端总砷含量10.42μg/g.As3＋的含量范围为0.84～1.08μg/g,As5＋的含量范围为6.87～8.99μg/g;As5＋含量表现为河端（8.63μg/g）高于海端（7.31μg/g）,As3＋则不明显.（3）有机质含量是影响本区域表层沉积物中砷及其他重金属含量分布的重要因素,粒径与砷及其他重金属显著相关性不强,影响较小.（4）柱状沉积物中总砷含量范围为9.15～13.61μg/g,随深度的变化不明显,人为污染程度较轻.（5）柱状沉积物中As3＋含量介于2.45～5.35μg/g之间,As5＋含量范围为5.58～11.77μg/g,二者含量随深度的增加而降低.     

Chemical speciation of arsenic in different marine organisms: Importance in monitoring studies

Arsenic is a widely distributed element in the marine environment. Inorganic and organic compounds have extremely different toxicological effects, and their characterization is thus of great utility when monitoring and assessing the impact of arsenic pollution. In this study both the levels of total arsenic and its chemical speciation were analyzed in several marine organisms collected from Cienfuegos Bay (Cuba) following an episode of acute As-contamination. Fish from the more impacted site were characterized by elevated concentrations of arsenic (up to 500 microg/g d.w.) and inorganic species represented the predominant forms in muscle tissues of these organisms.     

Uptake and metabolism of arsenate by anexic cultures of the microalgae Dunaliella tertiolecta and Phaeodactylum tricornutum

Axenic cultures of the microalgae species, Dunaliella tertiolecta and Phaeodactylum tricornutum were grown at arsenic (As) concentrations typically found in uncontaminated marine environments ( 2 µg L^− 1) under different phosphorus concentrations. D. tertiolecta accumulated higher arsenic concentrations (mean: 13.7 ± 0.7 µg g^− 1 dry mass) than P. tricornutum (mean: 1.9 ± 0.2 µg g−1 dry mass). Media phosphorus concentrations (0.6–3 mg/L) had little influence on microalgae growth rates or arsenic accumulation. Arsenic was present as lipid bound (29–38%; 4.2–9.5%), water-soluble (20–29%; 26–34%) and residue bound (41–45%; 57–69%) arsenic species in D. tertiolecta and P. tricornutum respectively. Hydrolysed lipids contained mostly glycerol arsenoribose (OH- ribose), dimethylarsinate (DMA) and inorganic arsenic (As(V)) moieties. Water-soluble species of microalgae were very different. D. tertiolecta contained inorganic arsenic (54–86%) with variable amounts of DMA (7.4–20%), arsenoriboses (5–25%) and traces of methylarsonate (MA) ( 1%). P. tricornutum contained mostly DMA (32–56%) and phosphate arsenoribose (PO₄-ribose, 23–49%) and small amounts of OH-ribose (3.8–6.5%) and As(V) (9–16%). Both microalgae contained an unknown cationic arsenic species. The residue fractions of both microalgae contained predominately inorganic arsenic (99–100%). These results show that at natural seawater arsenic concentrations, both algae take up substantial amounts of inorganic arsenic that is complexed with structural elements or sequestered in vacuoles as stable complexes. A significant portion is also incorporated into lipids. Arsenic is metabolised to simple methylated species and arsenoriboses.     

Changes in the northern Gulf of St. Lawrence ecosystem estimated by inverse modelling: Evidence of a fishery-induced regime shift?

Mass-balance models have been constructed using inverse methodology for the northern Gulf of St. Lawrence for the mid-1980s, the mid-1990s, and the early 2000s to describe ecosystem structure, trophic group interactions, and the effects of fishing and predation on the ecosystem for each time period. Our analyses indicate that the ecosystem structure shifted dramatically from one previously dominated by demersal (cod, redfish) and small-bodied forage (e.g., capelin, mackerel, herring, shrimp) species to one now dominated by small-bodied forage species. Overfishing removed a functional group in the late 1980s, large piscivorous fish (primarily cod and redfish), which has not recovered 14 years after the cessation of heavy fishing. This has left only marine mammals as top predators during the mid-1990s, and marine mammals and small Greenland halibut during the early 2000s. Predation by marine mammals on fish increased from the mid-1980s to the early 2000s while predation by large fish on fish decreased. Capelin and shrimp, the main prey in each period, showed an increase in biomass over the three periods. A switch in the main predators of capelin from cod to marine mammals occurred, while Greenland halibut progressively replaced cod as shrimp predators. Overfishing influenced community structure directly through preferential removal of larger-bodied fishes and indirectly through predation release because larger-bodied fishes exerted top-down control upon other community species or competed with other species for the same prey. Our modelling estimates showed that a change in predation structure or flows at the top of the trophic system led to changes in predation at all lower trophic levels in the northern Gulf of St. Lawrence. These changes represent a case of fishery-induced regime shift.     

原油WSF对三种海洋鱼类肝微粒体EROD活性的诱导和恢复的比较

研究了实验室条件下原油水溶性组分(WSF)暴露对黑鲷、黄鳍鲷和褐菖鲉肝微粒体EROD活性的剂量-效应,时间-效应和恢复过程。实验结果表明,在剂量诱导实验中,褐菖鲉肝EROD活性在原油WSF浓度为50μg/dm3时呈现生物统计学上的显著差异,而黑鲷和黄鳍鲷肝EROD活性在75μg/dm3时才呈现生物统计学上的显著差异;褐菖鲉肝EROD活性诱导倍数最高,但黑鲷的诱导浓度范围较广。在时间诱导实验中,在40μg/dm3原油WSF暴露下黄鳍鲷肝EROD活性在2 d时首先呈现显著差异;三种鱼肝EROD活性均在第4天达到最高,并呈现显著性变化,此后随着暴露时间的延长而逐渐下降并接近对照组水平。在恢复实验中三种鱼肝EROD活性下降并恢复到对照组水平。研究结果表明:对于石油污染物,黑鲷、黄鳍鲷和褐菖鲉肝EROD活性都可以作为污染生化效应监测指标,然而就三种鱼类比较而言,褐菖鲉最敏感,更适合于作为石油类污染及其生化效应,尤其是低剂量效应的监测生物。     

Fish Assemblages in Shallow Marine Caves of the Salento Peninsula (Southern Apulia, SE Italy)

Abstract. Fish assemblages of three shallow marine caves from the Salento Peninsula (Apulia, SE Italy) were investigated in July 2000. Data were collected in situ by using visual census. A total of nineteen fish species were recorded inside the caves. The species richness generally displayed a similar pattern in all three caves, decreasing from the entrance towards the innermost sections, whereas the patterns of total fish abundance differed among caves. Apogon imberbis (mainly represented by juveniles) was the most important species in terms of number of individuals (accounting for more than 85% of the censused fish) and showed a fairly even distribution inside the investigated caves. Without the numerical contribution of A. imberbis , fish abundance decreased from the entrance to the inner sections and this pattern was common to all three caves. Juvenile fishes of economic interest ( e. g., Diplodus vulgaris and Epinephelus marginatus ) were also recorded inside. The present study suggests that: (1) environmental constraints could affect distribution patterns in fish species richness and in the abundance of several fish along the axis of "blind caves" (with a single entrance), as already observed for sessile benthos and plankton assemblages; (2) shallow marine caves of the Salento Peninsula could exert the role of refuge and/or nursery for some littoral fish species during the adult and/or juvenile stages of their life histories.     

用X射线分析显微镜对海藻元素的研究Ⅰ.海藻的X射线荧光光谱

X射线分析显微镜(XGT-2000V, Horiba Co.,Japan,1993年制造)是一种新颖、快速的元素分析仪器,可以用来分析海藻中元素的组成特点。本研究对1997年4,5月在山东省威海市采集的22种海藻进行了研究,测定了海藻的Ⅹ射线荧光光谱(XRF),并根据Ⅹ射线特性荧光的能量分析海藻的主要元素组成。然后采用基本参数法(FP法)对每种海藻的主要元素进行了半定量分析。研究结果表明,Ⅹ射线分析显微镜可以快速观测海藻中的主要元素如钾、硫、钙、铁、锌、溴、锶等,是研究元素组成与化学种态的有效的非破坏分析手段。从Ⅹ射线荧光光谱可以看出,绿藻的特征元素是钾、钙、硫,孔石莼(Ulva pertusa)含有较多的铁元素,而浒苔则含有较多的溴元素。褐藻的特征元素除钾、钙、硫之外,还含有较多的锶元素。另外,酸藻 (Desmarestia viridis)含有大量的硫及溴元素,鼠尾藻(Sargassum thunbergii)、单条髓藻(Myelophycus simplex)及酸藻 (Desmarestia viridis)中尚含有较多的铁元素。红藻的特征是多种红藻均含有较大量的溴元素,例如波登仙菜(Ceramium kondai)、松节藻(Rhodomela confervoides)、多管藻(Polysiphonia urceolata)、石花菜(Gelidium amansii)及亮管藻(Hyalosiphonia caespitosa)。另外,珊瑚藻(Corallina pilulifera)中含有大量的钙质。     

三价砷和五价砷对鱼类乙酰胆碱脂酶的体外抑制比较

为开展水产品中三价砷的酶法快速检测工作,文中研究了三价砷(As3 + )、五价砷(As5+ )对8种鱼脑中乙酰胆碱酯酶(AChE)的抑制率。结果发现,在10 -7～10 -4mol/L范围内,草鱼和鲫鱼脑中AChE的抑制率与三价砷的浓度负对数值有较好的线性关系,相关系数都在0 .97以上;在10 -6～10 -4mol/L范围内,黑、马鲛、鲈鱼脑中AChE的抑制率与三价砷的浓度负对数值的线性相关系数大于0 .99。对于三价砷,由IC50 得到AChE的敏感性为:美国红鱼>草鱼,鲫,鲈鱼>黑,马鲛>鲤,白鲢。鱼种不同,AChE受到的三价砷、五价砷的抑制作用也不同。在浓度为10 -6～10 -4mol/L范围内,三价砷、五价砷对8种鱼脑中AChE的抑制作用存在极显著差异(p <0 .0 1) ,三价砷对AChE的抑制作用远大于五价砷的抑制作用。     

Seasonal variability of biological arsenic methylation in the estuary of the River Beaulieu

The observation of a strong seasonal variation of arsenic species found in the estuaries of the Rivers Beaulieu, Test and Itchen in central southern England is presented. The implications of such observations regarding the environmental biomethylation and fate of arsenic in natural waters are also discussed.     

Behaviour of arsenic on the continental shelf off the Gironde estuary: Role of phytoplankton in vertical fluxes during spring bloom conditions

The arsenic (As) cycle in the marine environment is known to be sensitive to biological activity. Within the scope of the National Coastal Oceanography Program, we undertook a specific study of the behaviour of this element in a water column on the continental shelf of the Bay of Biscay off the Gironde estuary during two oceanographic cruises conducted in May 1994 and May 1995. Various chemical forms were measured: arsenate (As3), arsenate (As5), monomethylarsenic (MMA), dimethylarsenic (DMA) and dissolved total As after ultraviolet mineralization. The net flux of total As from the Gironde estuary was evaluated as well as its effect on the concentration in surface marine waters. The vertical profiles in the coastal zone during a period of active primary production confirmed a certain analogy between arsenates and phosphates as well as the formation of As3 and DMA. The importance of organoarsenic species not directly accessible to the formation of volatile hydrides is demonstrated. Their presence modifies assessments, reducing the deficit of dissolved total As in the euphotic layer to just 5%. For particles, the As content in phytoplankton was estimated at 6 μg·g⁻¹ compared to 20 to 30 μg·g⁻¹ in iron- and aluminium-rich terrigenous particles. These results do not invalidate the role of phytoplankton in the speciation of dissolved As but indicate that their involvement in vertical transfers was apparently not predominant in the zone under study.     

我国马尾藻中砷的化学形态及其季节变化

于１９９６年３－８月在广东、广西及青岛沿海采集了部分代表性马尾藻,采用银盐分光光度法对新鲜样品中砷的化学形态,季节变化进行了研究。结果表明,广东,广西沿海马尾藻的总砷和无机砷含量较高,其中羊栖菜的无机砷含量占其总砷的５６．７３％,说明马尾藻富集无机砷的能力较强。青岛沿海鼠尾藻和海黍子的总砷含量在生长初期最低,成熟增至最高,无机砷占总砷的比例也表现出类似的季节变化,说明藻体砷含量与其生长周期有密切联     

Largemouth bass (Micropterus salmoides) and striped mullet (Mugil cephalus) as vectors of contaminants to human consumers in northwest Florida

The health benefits of regular consumption of fish and seafood have been espoused for many years. However, fish are also a potential source of environmental contaminants that have well known adverse effects on human health. We investigated the consumption risks for largemouth bass (Micropterus salmoides; n = 104) and striped mullet (Mugil cephalus; n = 170), two commonly harvested and consumed fish species inhabiting fresh and estuarine waters in northwest Florida. Skinless fillets were analyzed for total mercury, inorganic arsenic, polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F), polychlorinated biphenyls (PCBs), and organochlorine pesticides. Contaminant levels were compared to screening values (SV) calculated using U.S. Environmental Protection Agency (EPA) recommendations for establishing consumption advisories. Largemouth bass were found to contain high levels of total mercury at all sampling locations (0.37–0.89 ug/g) and one location exhibited elevated total PCBs (39.4 ng/g). All of the samples exceeded Florida fish consumption advisory trigger levels for total mercury and one location exceeded the U.S. EPA SV for total PCBs. As a result of the high mercury levels, the non-cancer health risks (hazard index–HI) for bass were above 1 for all locations. Striped mullet from several locations with known point sources contained elevated levels of PCBs (overall range 3.4–59.3 ng/g). However, total mercury levels in mullet were low. Eight of the 16 mullet sampling locations exceeded the U.S. EPA SV for total PCBs and two locations exceeded an HI of 1 due to elevated PCBs. Despite the elevated levels of total PCBs in some samples, only two locations exceeded the acceptable cancer risk range and therefore cancer health risks from consumption of bass and mullet were determined to be low at most sampling locations.     

Choice chamber experiments to test the attraction of postflexion Rhabdosargus holubi larvae to water of estuarine and riverine origin

Although the recruitment of larvae and juveniles of marine fishes into estuaries has been well documented, little is known about the factors governing the immigration of estuary-associated marine fishes into estuaries. Fishes have a well-developed sense of smell and it has been suggested by several workers that olfactory cues of freshwater or estuarine origin serve as stimuli, attracting larvae and juveniles of estuary-associated species into estuaries. Attraction of postflexion Rhabdosargus holubi larvae to estuary and river water from the Kowie estuarine system, South Africa, was measured using a rectangular choice chamber. In experiments, conducted during peak recruitment periods, larvae selected estuary and river water with a significantly higher frequency than sea water. This study, the first to assess the possible role of olfaction in the recruitment process of an estuary-associated marine fish species, demonstrates that larvae are able to recognise water from different origins, probably based on odour.     

The content and the oxidation state of arsenic and antimony in coastal water of Japan

The content and the oxidation state of arsenic and antimony in coastal seawater were determined coupled with chemical separation and neutron activation method. The contents of arsenic and antimony in coastal seawater were estimated to be 1.56–2.73g As/l, 0.25–0.57g Sb/l. Most parts of these elements exist as soluble ionic species, passing through 0.45 pore-size membrane filter, and at surface, 80–97% of arsenic occurs as arsenate and 70–94 % of antimony may occurs as antimonate. The vertical distribution of arsenite and arsenate is almost constant from the surface to 1,200 m depth. However the distribution of Sb(III) and Sb(V) is much more complicated with depth.