Stable isotopic ratios of lead in surface waters of the Central Pacific

The geographic variation in the isotopic composition of lead in surface waters of the central Pacific provides new evidence of the global anthropogenic perturbation of the element's cycle. Ratios of ²⁰⁶Pb/²⁰⁷Pb decrease from 1.196 in the northern hemisphere (19°N, 158°W) to 1.176 in the southern hemisphere (15°S, 150°W). This decrease parallels the geographic variation in surface concentrations of soluble lead which decrease from 13 ng kg^?1 at the northern station to 4 ng kg^?1 at the southern station. Both the ²⁰⁶Pb/²⁰⁷Pb and the ²⁰⁶Pb/²⁰⁸Pb ratios of those waters fit between the isotopic ratios of Australian (Broken Hill) and North American (Mississippi Valley) leads which are the predominant sources of leads in anthropogenic emissions to the Pacific Ocean basin.     

Lead pollution in subtropical ecosystems on the SE Gulf of California Coast: a study of concentrations and isotopic composition

Lead pollution was investigated in environmental matrices and biological indicators collected from two typical subtropical coastal ecosystems in the southeast Gulf of California, Mexico. Lead concentrations and isotopic compositions ((206)Pb/(207)Pb and (208)Pb/(207)Pb) were measured using high resolution inductively-coupled plasma-mass spectrometry (HR-ICP-MS) and thermal ionization mass spectrometry (TIMS), respectively. Lead in surface estuary sediments (10.0-34.2microgg(-1)) and particulate Pb (25.0-128.7microgg(-1), >98% of total Pb) in the water column were significantly higher than levels in natural bedrock soils (15.1+/-8.3microgg(-1)) and river runoff (1.9+/-1.4microgg(-1)). Aquatic plants had Pb concentrations between 2.5 and 7.2microgg(-1), while those in macroalgae ranged from 3 to 5microgg(-1). The ranges of mean Pb concentrations in the aquatic animals studied (ranges in microgg(-1)) were as follows: zooplankton 32+/-3, mussels 2.3-3.9, oysters 1.9-7.9, snail 2.0-7.7, barnacles 0.1-18.5, fish 1.4-8.9, crab 6.3-40.2 and polychaetae 8.5-16.7. Pb values in 20-40% of oyster and fish samples and in all samples of crab exceeded acceptable levels for a food source for human consumption. Pb isotope ratios (206)Pb/(207)Pb, (208)Pb/(207)Pb in biota ranged from 1.188 to 1.206 and 2.448 to 2.470, respectively. A plot of (206)Pb/(207)Pb versus (208)Pb/(207)Pb for the environmental and biological samples collected from two study areas indicates that they contain lead from ores mined in Mexico and used in the past to produce leaded gasoline in use until 1997, natural Pb weathered from the Sierra Madre Occidental mother rock, and the later influence of inputs from a more radiogenic source related to industrial activity in the United States. Statistical software IsoSource results revealed that the Pb contained in environmental matrices and biomonitors is mostly derived from gasoline (20-90%) and US emissions (10-40%).     

渤海中部沉积物铅来源的同位素示踪

本研究对渤海中部表层和柱状沉积物中Pb的含量和同位素进行了分析,研究了其时空分布规律,并探讨了其物质来源。结果表明,表层沉积物中Pb的含量为14.54×10-6~59.42×10-6,其含量在渤海湾近岸、黄河口附近、研究区的东北部较高,而在研究区的中部和渤海湾北部含量较低;Pb同位素207Pb/206Pb的值为0.8341~0.8489,208Pb/206Pb的值为2.0828~2.0980。岩心沉积物中Pb含量、同位素组成与表层沉积物相似,整体上较为稳定,但在1990s以来呈现增大的趋势。渤海中部沉积物中Pb以自然来源为主,黄河沉积物是其主要物质来源,但渤海湾北端则与滦河源物质或沿岸侵蚀相关;人类活动影响主要出现在1990s以后,与中国含Pb矿石的燃烧等工业活动相关,但影响微弱,仅在黄河口西北近岸海域、渤海湾等个别站位得到体现。     

Dispersal of natural and anthropogenic lead through submarine canyons at the Portuguese margin

Submarine canyons represent natural conduits for preferential transport of particulate material, including anthropogenic contaminants, from coastal zones directly to the deep sea. To assess related dispersal of natural and anthropogenic lead (Pb), we analyzed Pb concentrations and stable isotope ratios in surface sediments and sediment trap particulate material from the Portuguese margin Nazaré and Setúbal/Lisbon canyons. Geochemical data are integrated with previously obtained data on near-bottom hydrodynamics and processes and pathways of sediment transport. The two canyon systems are located in close geographic proximity to each other, but represent contrasting settings in terms of sediment input and down-canyon sediment transport processes.Concentration–isotope diagrams and three-isotope plots (²⁰⁶Pb/²⁰⁷Pb vs. ²⁰⁸Pb/²⁰⁶Pb) suggest binary mixing between natural and anthropogenic end members. The inferred isotopic signature of pollutant Pb (²⁰⁶Pb/²⁰⁷Pb=1.143 [1.134–1.149, 95% confidence interval]) is most consistent with industrial Pb; ongoing influence from gasoline Pb additives is at most of minor importance. Two proposed natural end members most likely bracket the isotopic signature of natural Pb. Accordingly, binary mixing calculations indicate that on average 20–45% vs. 35–55% of total Pb is derived from anthropogenic sources in the Nazaré and Setúbal–Lisbon canyon systems, respectively. Enhanced anthropogenic influence in the latter area is consistent with its proximity to heavily populated and industrialized areas and with sediment input from the Tagus and Sado rivers, potential major carriers of pollutant particles. In both canyon systems, the anthropogenic component generally decreases with increasing water depth.Isotopic signatures of sediment trap particulate material are generally consistent with surface sediment data at similar water depth, but show large variability in the upper Nazaré canyon and major deviations from surface sediments in the lower canyon. In the lower canyon, Pb isotopic ratios of sediment trap particulate material mostly reflect low pelagic fluxes from the overlying water column, whereas surface sediment signatures are dominated by episodic down-canyon mass transport events. Such gravity flows appear to incorporate older (pre-industrial) material masking the isotopic signature of pollutant Pb. Large variability in the upper canyon reflects continuous sediment resuspension by bottom currents. Stronger average bottom currents are associated with higher ²⁰⁶Pb/²⁰⁷Pb ratios of sediment trap particulate material and hence decreased influence of pollutant Pb. This may reflect preferential resuspension of natural Pb at the canyon floor and/or additional remobilization of older, less-polluted sediment in adjacent areas such as the canyon walls.     

Seasonal and spatial variations in the partial pressure of carbon dioxide in a eutrophic brackish lake,Lake Hamana,Japan

The dissolved inorganic carbon and total alkalinity in the surface brackish waters of Lake Hamana were investigated monthly from October 2017 to September 2019 at 14 stations. The partial pressure of carbon dioxide (pCO₂) in the surface water ranged from 29 to 1476 μatm and was undersaturated for atmospheric CO₂ during the observation periods, although most coastal waters were net source areas because of the large amount of terrestrial organic and inorganic carbon input. Since there was a strong negative correlation between pCO₂ and the dissolved oxygen, seasonal and temporal variations in pCO₂ were mainly derived from phytoplankton activity. The high phytoplankton activity induced by the effluents from sewage treatment plants, which was low in carbon and high in nitrogen. Therefore, in urbanized coastal waters with sewage treatment plants, such as the coastal waters of Japan, there is a possibility of shifting from weaker carbon dioxide source areas to sink areas. However, pCO₂ was oversaturated at the polluted river mouth, especially after high precipitation events due to the large carbon supply.

     

黄河三角洲贝壳堤的铅同位素特征

依据黄河三角洲王子岛海滩潮间带活贝壳和黄河三角洲贝壳堤中贝壳样品的铅同位素记录,初步探讨渤海湾南部最近6000多年来海水铅同位素变化特征及其环境意义,发现：①黄河三角洲贝壳堤中贝壳的铅同位素变化较大,^206Pb／^204Pb范围在18．207～18．648之间,平均值18．470;^207Pb／^204Pb在15．36～15．757之间,平均值15．619;^208Pb/^204Pb在37．947～38．945之间,平均值38．599。②渤海湾南部1．5～2．0kaBP海水放射性成因稳定铅同位素^206Pb、^207Pb、^208Pb相对于现在王子岛海滩潮间带海水亏损。③总体上讲,渤海湾南部4．5～6．0kaBP海水放射性成因稳定铅同位素相对于1．5～2．0kaBP的富集。④黄河三角洲贝壳堤中多数贝壳样品的铅同位素分布在海洋沉积物的范围内,但少数样品分布异常,其^206Ph／^204Pb、^207Pb/^204Pb,^208Pb/^204Pb偏低,可能是受陆地或相邻海区的玄武质中铅的输入的影响。     

Identification of Pb sources in Yellow Sea sediments using stable Pb isotope ratios

Rapid economic developments in East Asian countries have inevitably resulted in environmental degradation in the surrounding seas, and concern for both the environment and protection from pollutants is increasing. Identification of sources of contaminants is essential to environmental pollution management. In this study, the provenance of anthropogenic lead (Pb), a major pollutant of Yellow Sea sediments, was determined for river mouth sediments, including those of the Changjiang, Huanghe, Han, and Geum Rivers, and for age-determined shelf core sediments through the measurement of Pb isotope ratios in the HCl-leached fraction using multi-collector inductively coupled plasma-mass spectrometry (MC ICP/MS). Anthropogenic Pb has accumulated in shelf core sediments since 1910, and its isotope ratios were estimated as 0.863–0.866 and 2.119–2.125 for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively, from the mixing relationships of the two endmembers. River mouth sediments exhibited enough distinction in anthropogenic Pb isotope ratios to be discriminated: 0.874 (2.144) in the Huanghe, 0.856 (2.129) in the Han, 0.857 (2.122) in the Geum, and 0.854 (2.101) in the Changjiang for ²⁰⁷Pb/²⁰⁶Pb (²⁰⁸Pb/²⁰⁶Pb), respectively. Although isotope ratios of geogenic Pb in sediments dating before 1910 showed narrow ranges (0.842–0.845 and 2.088–2.100 for ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively), distinct isotope ratios in each core permitted source identification of sediments in the Yellow Sea based on geographic locations and the geogenic Pb of each river. By comparing the isotope ratios of the estimated anthropogenic Pb to source-related materials, the provenances of anthropogenic Pb in Chinese river sediments were presumed to be Chinese coal or ore, which is also a major source of atmospheric particulate Pb. The anthropogenic Pb in the shelf core sediments in the northern Yellow Sea originated from northern Chinese cities such as Beijing and Tianjin through atmospheric pathways. Pb isotope ratios indicated that Pb in Korean river sediments was characteristic of local Korean ores.     

Decline in heavy metal contamination in marine sediments in Jakarta Bay,Indonesia due to increasing environmental regulations

The ²¹⁰Pb geochronology, heavy metal concentrations (Zn, Cu, and Pb), and stable Pb isotope ratios (²⁰⁶Pb/²⁰⁷Pb) of three sediment cores collected from Jakarta Bay were analyzed to decipher the history of heavy metal contamination in the period 1900–2006. The chemical and isotopic analyses clearly suggest that anthropogenic metal accumulation in the sediments began in the 1920s and increased greatly from the 1970s until the end of the 1990s. From the end of the 1990s to 2006, accumulation rates were constant or decreased for Zn and Pb near the coastal industrialized area. Comparison of economic data and sociological information suggests that the decline in the concentrations of heavy metals could be attributed to the stricter environmental regulations which were enforced at the end of 1990s. However, metal contamination is currently still an important cause of concern in dealing with environmental preservation and protection in Jakarta Bay.     

Lead contamination of small cetaceans in European waters--the use of stable isotopes for identifying the sources of lead exposure

Lead concentrations and isotopic composition have been measured in bone and teeth of small cetaceans belonging to three species (Delphinus delphis, Phocoena phocoena and Stenella coeruleoalba), to evaluate the toxicological risk and to determine sources of lead in the European waters. Lead concentrations, far lower than threshold value inducing toxic effects in human, were higher in teeth than in bones, but highly correlated between the two tissues (r=0.92, p<0.001). Large variations of 206Pb/207Pb values in bone tissue showed that cetaceans must be submitted to various atmospheric influences. No geographical differences appeared which is consistent with studies on their distribution indicating seasonal movements between Brittany waters and the Bay of Biscay. The negative correlation between 206Pb/207Pb ratios and age of the individuals reflected the decrease in the production of alkyl lead in Europe, i.e., the increasing use of unleaded gasoline.     

A sensitive and rapid method for analysis of dissolved mono- and polysaccharides in seawater

A spectrophotometric method is described for the determination of dissolved mono- and polysaccharides in seawater. It is based upon the well known alkaline ferricyanide reaction, but uses the reagent 2,4,6-tripyridyl-s-triazine (TPTZ) to give a strongly colored complex with the reduced iron. The method has been tested on model carbohydrates and other compounds, and also on natural samples of coastal and oceanic waters. Total carbohydrate content of the natural samples ranged from 5.2 to 25.1 μmol glucose-Cl⁻¹. The coefficient of variation was typically below 6% for values near 17 μmol Cl⁻¹ and approximately 10% for values near 3.5 μmol Cl⁻¹.     

Distributions, sources and atmospheric fluxes of nitrous oxide in Jiaozhou Bay

The distributions, sources and atmospheric fluxes of nitrous oxide (N₂O) in the seawater of Jiaozhou Bay were investigated during four surveys in 2003 to evaluate this area as a source of N₂O to the atmosphere. N₂O concentrations in both the surface and bottom waters of Jiaozhou Bay showed obvious variability with both seasons and tidal cycles. Atmospheric fluxes of N₂O in Jiaozhou Bay showed seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of N₂O from the bay was estimated to be 1.09 × 10⁶–2.23 × 10⁶ mol yr⁻¹. N₂O in the water column of Jiaozhou Bay was found to come from several external sources including riverine water, sewage water and groundwater input, among which the riverine input was dominant while the groundwater input was rather limited. The spatial variation in distribution and atmospheric fluxes of N₂O in Jiaozhou Bay was influenced by the input of polluted river waters and sewage effluent along the eastern coast, which highlights the effects of human impacts on N₂O emission rates.     

Isotope dilution measurement of inorganic chromium(III) and total chromium in seawater

A reproducible, low-blank, isotope-dilution technique for the determination of inorganic Cr(III) and total dissolved chromium in seawater has been developed. Analysis of coastal water from Brittany, France, confirms that inorganic Cr(III) exists in excess of the thermodynamic equilibrium value calculated from the model of Elderfield (1970). A vertical profile of total chromium at 13°N on the East Pacific Rise confirms the general features of Cr behaviour: slight depletion at the surface (Cr = 2.0 nmol l⁻¹ compared to 2.6 nmol l⁻¹ below 1000 m) and bottom excess possibly due to Cr (III) release from sediments (up to 15.8 nmol l⁻¹). A maximum enrichment of six times the average seawater value is obtained in hydrothermal waters. The chromium content of metalliferous sediments is mainly due to scavenging from the water column; input of chromium into the ocean through hydrothermalism is negligible.     

Mercury distribution in seawater in Minamata Bay and the origin of particulate mercury

Horizontal and vertical distributions of mercury were determined in seawater in Minamata Bay and Yatsushiro Sea. The concentrations of total and particulate mercury respectively ranged from 56–285 ng l^–1 and 2.1–506 ng l^–1. They were both highest in the inner most part of Minamata Bay where the sediment was most heavily polluted, and decreased with increasing distance from there. Vertically, an evident increase in concentration was observed near the bottom. A good agreement was found between the mercury content in suspended matter and that in fine sediment particles.These facts show that the particulate mercury is supplied mostly from the bottom sediment, and that it is spreading offshore with dispersing in seawater. This process would eventually result in the pollution of sediment in Yatsushiro Sea.     

Arsenic in seawater and brown algae of the Baltic and the North Sea

A long-term study within the pilot environmental specimen bank programme of the Federal Republic of Germany on arsenic levels in coastal and open seawater and their reflection in the brown seaweed (Fucus vesiculosus) has been performed. Dissolved arsenic was on average 0.76 (range 0.45–1.11) μgl⁻¹ for 17 sampling stations in the Baltic Sea, whereas contents of dissolved arsenic are somewhat higher in shallow waters of the coastal zone of the North Sea. Total arsenic levels in algae ranged up to 40 mg kg⁻¹ (dry weight) and showed for the four locations studied obvious seasonal variations for comparatively nonpolluted or nondisturbed locations only. However, probably due to biological influences, the results obtained so far indicate that composite samples integrating a one year period are supposed to be the best strategy for future environmental specimen banking. Using a new efficient speciation technique the percentage of chemically stable organoarsenic compounds in the investigated algae has been found to be 95% of the total arsenic content and thus somewhat lower than in teleost fish. For comparison, typical data for a few other algae species from the Baltic and the Mediterranean Sea are also shown.     

Recent sudden decrease of lead in Adriatic coastal seawater during the years 2000–2004 in parallel with the phasing out of leaded gasoline in Italy

In parallel with the process of lead removal from gasoline in Italy, a research programme was undertaken to study the lead content of Adriatic coastal seawater. In the period 2000–2004 seawater was collected systematically at three sites along the coast line close to the city of Ancona: (i) the mouth of the River Esino, (ii) an area close to the Api refinery and (iii) Portonovo beach, a less impacted zone located along the coast of Mt. Conero. All samples were analyzed by Square-Wave Anodic-Stripping Voltammetry (SWASV). The results show that dissolved Pb content in coastal seawater diminished from an overall median value of 0.25 nmol/L in 2000–2001 to 0.12 nmol/L in 2003–2004, with a decrease of about 50% (statistically significant at 95% significance level). This decrease has been correlated to the concurrent decrease of lead consumption in gasoline in Italy which led to a reduction of ~ 65% Pb emissions into the atmosphere in the same period (r = 0.8791, p < 0.05).     

Cadmium and phosphate in coastal Antarctic seawater: Implications for Southern Ocean nutrient cycling

Cadmium is a biologically important trace metal that co-varies with phosphate (PO₄³⁻ or Dissolved Inorganic Phosphate, DIP) in seawater. However, the exact nature of Cd uptake mechanisms and the relationship with phosphate and other nutrients in global oceans remain elusive. Here, we present a time series study of Cd and PO₄³⁻ from coastal Antarctic seawater, showing that Cd co-varies with macronutrients during times of high biological activity even under nutrient and trace metal replete conditions. Our data imply that Cd/PO₄³⁻ in coastal surface Antarctic seawater is higher than open ocean areas. Furthermore, the sinking of some proportion of this high Cd/PO₄³⁻ water into Antarctic Bottom Water, followed by mixing into Circumpolar Deep Water, impacts Southern Ocean preformed nutrient and trace metal composition. A simple model of endmember water mass mixing with a particle fractionation of Cd/P (α_Cd–P) determined by the local environment can be used to account for the Cd/PO₄³⁻ relationship in different parts of the ocean. The high Cd/PO₄³⁻ of the coastal water is a consequence of two factors: the high input from terrestrial and continental shelf sediments and changes in biological fractionation with respect to P during uptake of Cd in regions of high Fe and Zn. This implies that the Cd/PO₄³⁻ ratio of the Southern Ocean will vary on glacial–interglacial timescales as the proportion of deep water originating on the continental shelves of the Weddell Sea is reduced during glaciations because the ice shelf is pinned at the edge of the continental shelf. There could also be variations in biological fractionation of Cd/P in the surface waters of the Southern Ocean on these timescales as a result of changes in atmospheric inputs of trace metals. Further variations in the relationship between Cd and PO₄³⁻ in seawater arise from changes in population structure and community requirements for macro- and micronutrients.     

The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

Isotope ratios of Pb/Pb in eelgrass, Zostera marina, indicate sources of Pb in an estuary

We deployed hydroponic eelgrass, Zostera marina L., to test its use as a sentinel accumulator and indicator of the source of water-borne lead (Pb) contamination in the marine environment. Eelgrass was deployed unrooted in the water column in the vicinity of the Portsmouth Naval Shipyard, located on Seavey Island in Portsmouth Harbor of New Hampshire and Maine, offshore from seepage sites near the Jamaica Island landfill (JIL). Deployed eelgrass, water samples from seepage sites, and sediment from the deployment sites were analyzed for Pb concentration and stable Pb isotopic composition. Isotopic composition was used to distinguish recent anthropogenic Pb inputs from background Pb in the estuary. Isotope ratios indicated that two groundwater seeps were a source of recent anthropogenic Pb (i.e. industrial Pb from the landfill) to Jamaica Cove. The eelgrass that showed the strongest presence of industrial Pb (having the lowest ²⁰⁶Pb/²⁰⁷Pb) was closest to a high volume seep that drained from the JIL and had a similar isotope signature as well as elevated Pb concentrations. These data confirm a source of water-borne industrial Pb in the estuary and show that eelgrass can function as a sentinel accumulator of Pb from anthropogenic sources.     

ComparativeP-postlabeling analysis of DNA Adducts in Perch (Perca fluviatilis) from unpolluted and polluted areas in Swedish coastal waters

Perch (Perca fluviatilis), were sampled from unpolluted and polluted areas in Swedish coastal waters. The level of aromatic/hydrophobic DNA adducts in liver tissue was analyzed using the nucleas P1 version of the³²P-post-labeling assay. The level of total adducts measured in the individual fish from polluted areas was between 6 and 22 nmol of adducts/mol of nucleotides, and in the fish from the reference area between 0.2 and 0.6 nmol of adducts/mol of nucleotides.     

Tracing the origin of Pb using stable Pb isotopes in surface sediments along the Korean Yellow Sea coast

To investigate the factors controlling lead (Pb) concentration and identify the sources of Pb in Yellow Sea sediments along the Korean coast, the concentration of Pb and Pb isotopes in 87 surface and 6 core sediment samples were analyzed. The 1 M HCl leached Pb concentrations had a similar geographic distribution to those of fine-grained sediments, while the distribution of residual Pb concentrations resembled that of coarse-grained sediments. Leached Pb was presumed to be associated with manganese (Mn) oxide and iron (Fe) oxy/hydroxide, while residual Pb was associated with potassium (K)-feldspar, based on good linear relationships between the leached Pb and the Fe/Mn concentrations, and the residual Pb and K concentrations. Based on a ratio–ratio plot with three isotopes (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) and the geographic location of each sediment, sediments were categorized into two groups of samples as group1 and group2. Group 1 sediments, which were distributed in Gyeonggi Bay and offshore (north of 36.5°N), were determined to be a mixture of anthropogenic and natural Pb originating from the Han River, based on a ²⁰⁸Pb/²⁰⁶Pb against a Cs/Pb_leached mixing plot of core and surface sediments. Group 2 sediments, which were distributed in the south of 36.5°N, also showed a two endmembers mixing relationship between materials from the Geum River and offshore materials, which had very different Pb concentrations and isotope ratios. Based on the isotopes and their concentrations in core and surface sediments, this mixing relationship was interpreted as materials from two geographically different origins being mixed, rather than anthropogenic or natural mixing of materials with the same origin. Therefore, the relative percentage of materials supplied from the Geum River was calculated using a two endmembers mixing model and estimated to be as much as about 50% at 35°N. The spatial distribution of materials derived from the Geum River represented that of fine-grained sediments originating from the Geum River. It was concluded that Pb isotopes in sediments could be used as a tracer in studies of the origin of fine-grained sediments along the Korean Yellow Sea coast.