The automatic determination of iodate- and total-iodine in seawater

The development of procedures for the determination of iodate- and total-iodine content of seawater, which use a Technicon Auto-Analyser, is described. In both procedures the appropriate iodine species is first converted to iodate-iodine. Then, this is reacted with acid and excess iodide to give the iodonium ion, I₃^?, which is detected spectrophotometrically. In the total-iodine procedure the pre-oxidation is accomplished using bromine water. In the iodate procedure a pre-oxidation step using iodine-water can be included. It is anticipated that this will be used to test for the presence of naturally occurring reducing agents in seawaters, which by their action on iodonium ions could lead to an underestimate in iodate concentration. Seawaters, particularly coastal and surface oceanic ones, are known to contain iodine-reducing substances. Therefore, the validity of results obtained through the iodometric method for iodate must remain in some doubt until these tests have been made. The use of this method on anoxic waters which contain sulphides appears to be a prime example of where caution should be observed. The iodate procedure, both with and without pre-oxidation, has been tested on approximately 50 samples of waters from the Eastern Pacific Ocean; these waters did not appear to contain significant amounts of reducing agents. In a similar study, it was found that there was no significant difference between the results obtained by the new total-iodine procedure and an earlier automatic catalytic one.     

A high sensitivity method for the determination of nanomolar concentrations of Nitrate and Nitrite in seawater with a technicon autoanalyzer II

A high sensitivity manifold for the determination of trace quantities (nanomolar concentrations) of nitrate+nitrite and nitrite alone is described. The method uses a classical Technicon AutoAnalyzer II usually employed for shipboard analysis. A reproducibility of ± 1 nmol dm⁻³ for nitrate plus nitrite and nitrite alone was obtained, with an analytical rate of 40 samples h⁻¹.     

A colorimetric procedure for the determination of aldehydes in seawater and in cultures of methylotrophic bacteria

A spectrophotometric procedure for the determination of aldehydes was optimized for use in seawater, it involves the sequential reaction of aldehydes with 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) and FeCl₃ to produce a colored compound which is soluble in 50% acetone. The standard curve obeyed Beer's law to 90 μM formaldehyde in 0.7 m NaCl. The molar absorptivity of 21 800 absorbance units μM^?1 cm^?1 at 635 nm was not affected by changes in salinity. The limit of detection was 180 nM HCHO l^?1 when a pathlength of 1 cm was used, and 72 nM HCHO l^?1 when a pathlength of 5 cm was used.The MBTH procedure was used to compare formaldehyde production in cultures of the marine methanotroph, Methylomonas pelagica, growing on methane or methanol. The average rate of formaldehyde production, normalized to cell number, was almost 20 times greater in cultures grown on methanol than in cultures grown on methane.A depth profile of aldehyde concentrations from a station in the Peru upwelling region (10°S, 79°W) showed one peak in the oxygen gradient in the photic zone (80 m), two in the oxygen minimum (200 and 300 m), and one in the oxygen gradient below the minimum (800m). Aldehyde concentrations ranged from 0.6 to 8.8 μM formaldehyde equivalents l^?1. Except for the maxima where the aldehydes account for 13–15% of expected DOC concentrations, the background level of aldehydes was approximately 1% of DOC.     

Coulometric TCO2 analyses for marine studies; an introduction

Progress in the introduction of coulometry for the analysis of total carbon dioxide (TCO₂) in marine waters is described. An extractor—stripper removes CO₂ that is measured coulometrically by the quantity of electricity (coulombs) used to electrogenerate OH^? ions for the titration of the acid formed by the reaction of CO₂ and ethanolamine. The equivalence point is detected photometrically with thymolphthalein as the indicator, and Faraday's Law relates coulombs to equivalents of titrant generated and CO₂ determined so that there are no standard curves needed or titrants to standardize or store. Accuracy was determined by adding gelatin capsules containing 100–1500 μg C of pure CaCO₃ into the stripper, and accuracies of better than ± 1 μg C were achieved. The best precision for natural seawater (± 1 standard error) of ± 0.5 μmol l^?1 was found for 17 samples of Bermuda coastal waters having a mean TCO₂ of 2007.2 μmol l^?1 (0.05% CV). Sources of error and precautions are discussed. This method, which has been used successfully at sea, can be used to study a variety of marine phenomena involving TCO₂.     

Studies on the determination of inorganic iodine in seawater

Existing methods for the determination of the various forms of iodine present in seawater are laborious or unwieldy in use. This paper describes modified forms of the iodate and total iodine methods described by Barkley and Thompson (1960), a spectrophotometric procedure for iodate determination derived from Johannesson's (1958) work, and an automatic method for total iodine determination. Procedures for iodate and total-iodine determination which are suitable for use aboard ship, are recommended. Both procedures for iodate determination returned a standard deviation close to 0.5 μg/l when several replicate samples of a seawater containing approximately 30 μg/l of iodate-iodine were analysed. The automatic method for total iodine determination yielded a standard deviation of 0.8 μg/l by the repeated analysis of a seawater containing a total of approximately 50 μg/l of iodine. Suitable methods for the filtration and storage of seawater are also described.     

‘Reactive’ and ‘unreactive’ iodine in seawater — A possible indication of an organically bound iodine fraction

An iodine component in seawater, which is ‘unreactive’ to the total inorganic method described by Truesdale and Spencer (1974), has been discovered. The component is measured as the increase in ‘reactive’ iodine that accompanies irradiation of seawater with high-intensity UV light. The highest concentration recorded for an inshore water was $\text{5.2 ± 0.5}\text{μg/l}$. As some known organic-iodine compounds behave in a similar manner to UV irradiation, it is suggested that the ‘unreactive’ iodine is organically bound iodine.     

Dissolved iodine in waters overlying and in the Orca Basin,Gulf of Mexico

The distribution and speciation of iodine, a biophilic redox-sensitive trace element, in waters overlying and in the Orca Basin, Gulf of Mexico, which contains hypersaline, anoxic and yet non-sulfide-bearing brine have been determined. The distribution of iodate and iodide in the oxic waters overlying the anoxic brine are similar to those reported in other oceans. However, in the oxic-anoxic mixing zone, iodate disappears while the concentration of iodide reaches a maximum of 8.1 μM, the highest concentration ever reported in open oceans. There is also a maximum in specific iodine of 30.7 nM‰^?1 at this depth. Specific iodine in oxic seawater is only about 10–14 nM ‰^?1. These features may be explained by the preferential dissolution of biogenic particles that have accumulated in a strong pycnocline. In the anoxic brine proper, the concentration of iodide is 3.8 μM and can be explained almost entirely by the simultaneous mobilization of chloride and iodide during the dissolution of evaporite beds as the specific iodine of 14.5 nM‰^?1 is only slightly higher than those observed in the oxic waters.     

Individual and interactive effects of environmental stress on the embryonic development of the Pacific oyster, Crassostrea gigas. I. The toxicity of copper and silver

Pacific oyster, Crassostrea gigas Thunberg, embryos were exposed to copper and silver salts, alone and in combination, through the completion of embryogenesis and metal effects upon normal embryonic development were monitored. Copper concentrations throughout the test period ranged from 0·0 to 12·0 μg litre^?1 while silver concentrations were between 0·0 and 18·0 μg litre^?1.Administered individually, silver and copper yielded decreasing per cent normal embryonic development with increasing metal concentration. However, both metals exhibited ‘plateaus’ wherein per cent normal embryonic development did not decrease with increasing metal concentration until a particular concentration was attained. A rapid decrease in per cent normal embryonic development occurred with increasing metal concentrations greater than 6·0 μg litre^?1 copper and 11·0 μg litre^?1 silver.The dose-response patterns of copper and silver appear to be similar with copper exhibiting somewhat greater toxicity. At a copper concentration of 10 μg litre^?1 only 50% of the embryos could be considered normally developed, whereas silver concentrations between 16·0 and 18·0 μg litre^?1 yielded 50% normal embryonic development.Response surface methodology indicated that copper and silver interacted additively, with embryonic development affected to a much greater degree by copper than by silver. Optimum development of Crassostrea gigas embryos was greatly influenced by copper concentrations and occurred at all silver concentrations wherein the corresponding copper concentrations were 6·0 μg litre^?1 or less. Above 6·0 μg litre^?1 copper, per cent normal embryonic development was significantly reduced, even at the lowest tested silver concentrations.Abnormal embryos exhibited retarded shell growth, reduced size and extremely erratic swimming behaviour. These sublethal effects probably have a biochemical origin and would limit the organism's capacity to feed properly, escape predation and develop normally, thereby reducing the chances of successful metamorphosis and recruitment into the adult population.     

Dissolved carbohydrates in seawater. II,A spectrophotometric procedure for total carbohydrate analysis and polysaccharide estimation

A procedure is described which adds a hydrolysis step to the Johnson and Sieburth 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) assay for total dissolved monosaccharides. The advantages of the monosaccharide test are retained in the total carbohydrate test, giving nearly equivalent responses for a variety of combined carbohydrates. A total sample of 50 ml is adequate for both total carbohydrate and monosaccharide assays which permit the estimation of polysaccharide by difference. Values for Narragansett Bay and adjacent waters ranged from 452 to 2023 μg l^?1 for total dissolved carbohydrate, 272 to 1353 μg l^?1 for polysaccharide, and 153 to 814 μg l^?1 for monosaccharide, which accounted for 6–18%, 4–13%, and 2–5% of the total dissolved carbon, respectively. We suggest that this is a sensitive and precise procedure which will be useful for investigating the distribution of dissolved carbohydrates in seawater and factors which affect its production, distribution and utilization.     

The determination of Cd,Cu, Fe,Ni, Pb and Zn in Baltic Sea water

Cd, Cu, Fe, Ni, Pb and Zn were determined in 123 samples from the Baltic Sea proper. The trace metals were extracted directly on board the vessel, using a dithiocarbamate-Freon procedure. Final analyses of the extracts are performed onshore by atomic absorption spectrometry.Similar trace-metal concentrations are found in different areas of the Baltic proper. Most values fall in the following ranges: Cd, 30–60 ng 1^?1; Cu, 0.6–1.0 μg 1^?1; Fe, 0.3–0.9 μg 1^?1; Ni, 0.6–0.9 μg 1^?1; Pb, 0.05–0.2 μg 1^?1; and Zn, 1.5–3.5 μg 1^?1. The metal-concentrations are generally independent of depth. However, copper exhibits a small but significent decrease in concentration below 80 m.Filtration did not affect trace-metal concentrations, with the exception of iron in waters from lower layers. Similarly, storage under acid conditions was shown to affect only the concentration of iron. An electro-chemical technique was also used to determine Cu in some samples.     

An automated photochemical method for the determination of dissolved organic carbon in sea and estuarine waters

An improved version of Ehrhardt's (1969) method for the analysis of dissolved organic carbon is described. The method, which is automated, determines the carbon dioxide with a non-dispersive infra-red analyser. The conditions of photo-oxidation have been examined in order to achieve maximum performance. It was found that careful attention needed to be paid to U-V source, “oxygen source”, pH and time or irradiation. The completeness of the method was examined by three independent procedures. We concluded that in all cases the extent of oxidation of organic material was in excess of 98%. Typical performance figures were: precision ±2.5% above 2.0 mg C l^?1, approaching 0.03 mg C l^?1 below 1.0 mg Cl^?1; blank, equivalent to 0.3 mg C l^?1; sampling frequency, 10 samples per hour. The lower limit of sensitivity is mainly governed by the blank. The upper limit of the method is greater than 40 mg C l^?1.A wholly continuous modification of the method has been devised which permits on line analyses. An attentuated version of the method has been used for the analysis of total carbonate.The present and other published methods for the analysis of dissolved organic carbon in natural waters are discussed in relation to one another.     

Effects of organic pollutants on methanogenesis,sulfate reduction and carbon dioxide evolution in salt marsh sediments

Anaerobic salt marsh sediments were amended with a variety of organic pollutants and the effects on methanogenesis, sulfate reduction and carbon dioxide evolution were examined. Addition of 1000 μg g^?1 (dry weight sediment) Arochlor 1221, lindane, endrin, benzene and phenanthrene resulted in no significant effects on the activities studied. Methanogenesis was inhibited by 1000 μg g^?1toxaphene, PCP, chlordane, naphthalene, DDT, Kepone and heptachlor and by 100 μg g^?1 PCP and toxaphene. At 1000 μg g^?1 naphthalene and toxaphene and 100 μg g^?1 PCP, a period of initial inhibition of methanogenesis was followed by stimulation relative to controls. Arochlor 1254 (1000 μg g^?1) and Temik (500 and 10 μg g^?1) stimulated methanogenesis from the outset. Temik at 500 μg g^?1 gave the greatest stimulation of methanogenesis (900% of controls) of any of the compounds studied. Sulfate reduction was inhibited by 1000 μg g^?1 PCP, toxaphene, naphthalene and chlordane and by 500 μg g^?1 atrazine and 100 μg g^?1 heptachlor. Sustained inhibition of sulfate reduction by naphthalene, toxaphene and PCP may have contributed to the stimulation of methanogenesis. Carbon dioxide evolution was not significantly affected by most of the compounds studied except for 100 μg g^?1 PCP and 1000 μg g^?1 aphthalene, each of which gave significant inhibition in only one of three experiments.Concentrations of individual organic pollutants required to cause observable effects were high. It is concluded that, except for highly polluted sediments, methanogenesis, sulfate reduction and CO₂ evolution would not be affected by the compounds studied here at concentrations typically found in the environment.     

Determination of volatile fatty acid turnover rates in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates in organic-rich marine sediments were determined by measuring whole sediment VFA concentration and the corresponding first-order reaction rate constants. In order to measure VFA concentrations, bulk wet sediment samples were basified, freeze-dried, extracted with methanol, derivatized to form methyl esters of the VFAs, and analyzed by packed-column gas chromatography using hexanoic acid as an internal standard. The detection limits for acetate, propionate, iso-butyrate and butyrate were 1.0, 0.4, 0.2 and 0.2 μmol l^?1_s, respectively, for 600 ml samples. Rate constants for acetate and propionate were determined by anaerobically incubating samples at in-situ temperatures with tracer levels of ¹⁴C-labelled VFAs. Metabolized label was recovered as CO₂, CH₄, cellular material, water-soluble material, and VFA (ether-soluble) fractions. Apparent turnover rates measured during summer and winter in anoxic Cape Lookout Bight, North Carolina (U.S.A.) sediments were in the range of 19–330 μmol l^?1_s h^?1 for acetate and 0.7–7.0 μmol l^?1_s h^?1 for propionate.     

A comparative study of three methods for the determination of iodate in seawater

A comparative study of three methods for the determination of iodate-iodine in seawater is described. In one method the iodate is determined polarographically while in the others the iodate is determined colorimetrically as iodonium ions. In one of the colorimetric methods each sample is pre-treated with excess iodine-water in an attempt to eliminate suspected interference from naturally occurring reducing agents. The tests were conducted on a selection of open-ocean and near-shore waters with iodate concentrations ranging from 0 to 60 μg 1^?1-I. The tests indicated that the polarographic method and the colorimetric method without iodine-water give the more reliable measurement of iodate concentration. Also, the method with iodine water was found to be in error especially at low iodate concentrations. Reducing agents, if present, were found not to interfere significantly.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

Chemical determination of particulate nitrogen in San Francisco Bay. Nitrogen: chlorophyll a ratios in plankton

Particulate nitrogen (PN) and chlorophyll a (Chla) were measured in the northern reach of San Francisco Bay throughout 1980. The PN values were calculated as the differences between unfiltered and filtered (0·4 μm) samples analyzed using the UV-catalyzed peroxide digestion method. The Chla values were measured spectrophotometrically, with corrections made for phaeopigments. The plot of all $\text{PN}\text{Chl}\text{a}$ data was found to be non-linear, and the concentration of suspended particulate matter (SPM) was found to be the best selector for linear subsets of the data. The best-fit slopes of $\text{PN}\text{Chl}\text{a}$ plots, as determined by linear regression (model II), were interpreted to be the N: Chla ratios of phytoplankton. The Y-intercepts of the regression lines were considered to represent easily-oxidizable detrital nitrogen (EDN). In clear water ( < 10 mg l^?1 SPM), the N: Chla ratio was 1·07 μg-at N per μg Chla. It decreased to 0·60 in the 10–18 mg l^?1 range and averaged 0·31 in the remaining four ranges (18–35, 35–65, 65–155, and 155–470 mg l^?1). The EDN values were less than 1 μg-at N l^?1 in the clear water and increased monotonically to almost 12 μg-at N l^?1 in the highest SPM range. The N: Chla ratios for the four highest SPM ranges agree well with data for phytoplankton in light-limited cultures. In these ranges, phytoplankton-N averaged only 20% of the PN, while EDN averaged 39% and refractory-N 41%.     

Effects of some representative petroleum refinery effluent compounds on photosynthesis and growth of natural marine phytoplankton assemblages: Part 1—cresols

The effects of cresols on the photosynthesis and growth of natural marine phytoplankton assemblages from the Scripps Pier at La Jolla, California, USA were measured. In two experiments, in which dinoflagellates were the dominant algae, photosynthesis (measured by ¹⁴C uptake) was inhibited at concentrations > 100 μg litre^?1 and the concentration giving half-maximal photosynthesis was 10,000 μg litre^?1. In a third experiment, in which diatoms were dominant, photosynthesis was not inhibited until levels > 10,000 μg litre^?1 were reached and the half-maximal concentration was 20,000 μg litre^?1. These experiments suggested that dinoflagellates were more sensitive to cresols than diatoms. However, the reverse was true in an experiment using cultures. In a long-term growth experiment (natural assemblages from the Scripps Pier), only a level of 88,000 μg litre^?1 completely inhibited growth. There was a two-day lag in growth at 8500 μg litre^?1, but the algae recovered and grew as well as the controls which contained no cresols. This experiment was started with a mixed diatom-dinoflagellate-microflagellate population but only the diatoms grew. High concentrations of cresols (> 900 μg litre^?1) resulted in a decrease in the diatom Skeletonema costatum, compared with the controls. Otherwise there was no selection for resistant species. In these experiments, cresols were measured by extraction with methylene chloride from seawater followed by measurement by UV absorption. In all experiments cresol levels decreased with time. This was attributed to uptake by phytoplankton and bacterial degradation.     

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.     

Trace metals in the Göta river estuary

The concentrations of the trace metals Cd, Cu, Fe, Ni, Pb and Zn in the Göta River estuary have been investigated. The following metal fractions have been determined: acid-leachable, dissolved, labile and particulate.The estuary represents a salt wedge type estuary and is situated in a densely populated region of Sweden. The metal concentrations found for the dissolved fraction is in the range of what can be considered as background levels for freshwater. It is difficult to evaluate any estuarine processes other than conservative mixing for Cd, Cu, Ni and Zn. The dissolved levels in the freshwater end member are Cd, 9–25 ngl^?1; Cu, 1·1–1·4 μgl^?1; Fe, 20–75 μg l^?1: Ni, 0·7–0·9 μg l^?1: Pb 0·09–0·2 μg l^?1; and Zn, 6–7 μg l^?1:The results from the acid-leachable fraction show that at high suspended load the particles sediment in the river mouth. The trace metal levels in this fraction are subject to large variations.     

Teneurs en benzo 3,4 pyrène chez Mytilus edulis L. de l'estuaire et du golfe du Saint-Laurent

Blue mussels (Mytilus edulis L.) taken from 27 stations along the estuary and gulf of St. Lawrence were analyzed for their content in 3,4-benzopyrene. Most of the concentrations are below the detection limit for the analytical method, i.e. 0·15 μg kg^?1 (dry weight) and probably reflect the natural baseline level. However, mussels from two stations located at the mouth of Saguenay Fjord exhibit very high contents: 24 and 28·5μg kg^?1 (dry weight). A mussel transplantation experiment has shown that the entire Fjord is contaminated by anthropogenic 3,4-benzopyrene.