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We expanded the batch-to-batch offsets of The International Association for the Physical Sciences of the Oceans (IAPSO) Standard Seawater (SSW) batches P145–P163 by intercomparison measurements using salinometers. On the basis of our results, we recommend using the correction factors instead of the offsets to correct the batch-to-batch differences, especially for salinity data outside the range of 30–40 g kg −1 . We evaluated the expanded batch-to-batch correction factors by applying them to time series salinity data collected in the northwestern North Pacific Ocean and found that they are effective for detecting recent freshening (−0.6 ± 0.1 × 10 −3 g kg −1 decade −1 ) in the deep North Pacific, which might be related to a reduction of the formation rate of Antarctic Bottom Water. We also evaluated the SSW linearity pack by applying the batch-to-batch correction factors. Linearity errors of the salinometers estimated from decade resistance substituters were consistent with the results of the linearity pack measurements. To correct the linearity errors of a salinometer, it might be suitable to use the more detailed distribution of those estimated from the decade resistance substituter than the linearity pack measurements. Since the cause of large batch-to-batch differences is still unclear, a reference seawater that is more robust and stable than SSW might be necessary to establish a high-level of international comparability of salinity measurements; the Multiparametric Standard Seawater (MSSW) currently under development might be a candidate for such reference seawater, because MSSW is expected to be more stable than SSW not only in practical salinity but also in absolute salinity.

Seawater intrusion is recognised as a major factor affecting the quality of groundwater in coastal aquifers around the world. To determine the occurrence and extent of saline groundwater intrusion prevailing in the Heuningnes Catchment, a 2D resistivity imaging survey was carried out in three sites within the catchment. Eleven resistivity profile lines were conducted using the multi-electrode ABEM SAS resistivity meter system, employing the Wenner Array to map the extent of saline groundwater. A 2D resistivity image was acquired for these resistivity profile lines and the data were processed using Res2DINV software to produce the 2D inverse resistivity models. The interpretation of the resistivity models revealed three resistivity zones. The first zone is characterised by low resistivity (1–3 Ω.m); this represents an aquifer filled with saline water. The second resistivity zone has values ranging from (3–30 Ω.m); this represents a brackish saturated formation. The third resistivity zone denotes a sandy layer/sandstone saturated with freshwater having high resistivity values above 30 Ω.m. Geochemical analysis results of water samples at 11 locations along the electrical resistivity profile lines also suggest high salinity, indicated by high levels of Cl−, Na+, Total Dissolved Solids, and Electrical Conductivity. It is concluded that some parts of the study area are impacted by seawater intrusion, based on the lower resistivity of < 3 Ω.m and ionic ratios which were close to the standard seawater ratios for Na+/Cl− and SO42−/Cl−. In addition, the high ionic ratios of Na+/Cl− and SO42−/Cl− suggest that salinity in the area is a result of dissolution of evaporates and dilution of marine clays rich in sodium. Therefore, salinization in the study area is the result of combined processes. Integration approach proved to be significant in mapping saline groundwater in coastal aquifers. Integrated assessment of resistivity data, ionic analysis and chemical interpretation indicate that the study area is a transition zone from freshwater to saltwater and only few locations are actually impacted by seawater intrusion. The overall groundwater quality is not apt for human ingestion.

The determination of salinity by means of electrical conductivity relies on stable salt proportions in the North Atlantic Ocean, because standard seawater, which is required for salinometer calibration, is produced from water of the North Atlantic. To verify the long-term stability of the standard seawater composition, it was proposed to perform measurements of the standard seawater density. Since the density is sensitive to all salt components, a density measurement can detect any change in the composition. A conversion of the density values to salinity can be performed by means of a density–salinity relation. To use such a relation with a target uncertainty in salinity comparable to that in salinity obtained from conductivity measurements, a density measurement with an uncertainty of 2 g m−3 is mandatory. We present a new density–salinity relation based on such accurate density measurements. The substitution measurement method used is described and density corrections for uniform isotopic and chemical compositions are reported. The comparison of densities calculated using the new relation with those calculated using the present reference equations of state TEOS-10 suggests that the density accuracy of TEOS-10 (as well as that of EOS-80) has been overestimated, as the accuracy of some of its underlying density measurements had been overestimated. The new density–salinity relation may be used to verify the stable composition of standard seawater by means of routine density measurements.

Dissolved organic matter (DOM) in seawater, consisted of a complex mixture of compounds and accounted for about 90% of marine organic carbon, is an important part of the global carbon cycle and also a part of absolute salinity of seawater. As the components of DOM are non-ionized in seawater, electric conductivity measurement cannot observe its contribution to salinity, which could lead to measurement error in salinity. Salinity measurement based on optic refractive index could reveal contribution of all dissolved matters in seawater including both non-ionized and ionized components. In this paper, a comparative study of DOM contribution to the salinity measurement by optic refractive index method and electric conductivity method was carried out for the first time. Adding DOM, extracted from Aoshan Bay, Qingdao, China, into Chinese Standard Seawater, our experimental results showed an increase of optic refractive index at 1.19×10 -4 ± 4×10 -6 per 1g/kg of DOM, which corresponds to a practical salinity increase of 0.697 ± 0.036 PSU per 1 g/kg of DOM. While, the conductivity of seawater measured by a conductivity-temperature sensor showed a decrease of 0.00065 ± 0.00008 mS/cm per 1 g/kg of DOM, which corresponded to a decrease of salinity at 0.00052 ± 0.00007 PSU per 1 g/kg of DOM. By comparing the optic and electric measurement results, the contribution of non-conductive components in the dissolved organic matters to salinity could be distinguished, which has great significance for the measurement of absolute salinity, global carbon cycle etc.

Calcium (Ca2+) is an important major cation in seawater, which is closely related to the oceanic biogeochemistry cycle. Direct and accurate determination of Ca2+ concentration is required for a more comprehensive study of the carbonate system in seawater. Due to the high background concentration of Ca2+ in seawater and small variances of Ca2+ during CaCO3 precipitation and dissolution process, a precision of better than 0.1% (of approximately ±10 µmol/kg) is very much desired for carbonate chemistry related studies. In this study, a simple, non-toxic and labor-saving technique using ion chromatography (IC) has been developed to determine Ca2+ in seawater with an overall precision of better than 0.1%. This proposed method, using IAPSO standard seawater as a reference, can get a result within 15 min and only requires a small sample volume (~1 ml). The concentrations and flow rates of the eluent have been optimized to achieve the best chromatographic separation (20 mmol/L and 1.0 mL/min were selected in this study). Our work suggests that sample dilutions have no discernible effect on Ca2+ determinations. However, the measured Ca2+ concentration shows a linear decrease with the increasing Mg/Ca ratio in samples, which could be corrected by a derived formula to achieve high accuracy within 0.1%. This optimized method has been applied to the analysis of Ca2+ distribution in Southwest Indian Ocean and the laboratory study on the calcite precipitation in seawater.

We measured metabolism rates in a shallow, nitrogen-enriched coastal marine ecosystem on Cape Cod (MA, USA) during seven summers using an open-water diel oxygen method. We compared two basins, one directly receiving most of the nitrogen (N) load (“Snug Harbor”) and another further removed from the N load and better flushed (“Outer Harbor”). Both dissolved oxygen and pH varied greatly over the day, increasing in daylight and decreasing at night. The more N-enriched basin frequently went hypoxic during the night, and the pH in both basins was low (compared to standard seawater) when the oxygen levels were low, due to elevated carbon dioxide. Day-to-day variation in gross primary production (GPP) was high and linked in part to variation in light. Whole-ecosystem respiration tended to track this short-term variation in GPP, suggesting that respiration by the primary producers often dominated whole-system respiration. GPP was higher in the more N-loaded Snug Harbor. Seagrasses covered over 60 % of the area of the better-flushed, Outer Harbor throughout our study and were the major contributors to GPP there. Seagrasses covered 20 % of the area in Snug Harbor for the first 5 years of our study, and their contribution to GPP was relatively small. The seagrasses in Snug Harbor died off completely in the 6th year, but GPP remained high then and in the subsequent year. Overall, rates of phytoplankton GPP were relatively low, suggesting that benthic micro- and macro-algae may be the dominant primary producers in Snug Harbor in most years. Net ecosystem production in both Snug Harbor and the Outer Harbor was variable from year to year, showing net heterotrophy in some years and net autotrophy in others, with a trend towards increasing autotrophy over the 7 years reported here.

The hydrogeochemical and stable isotope compositions of aquitard porewater samples from three boreholes were investigated to determine the origin, salinization, and hydrochemical evolution of water in the North Jiangsu coastal plain, China. Three porewater groups were identified based on the water-bearing subsystems. The total dissolved solids (TDS) of porewater samples highly varied from 0.03 to 26.1 g/L. Molar Cl/Br ratios and δ18O and δ2H data indicate that the source of Group 1 salinized porewater was the Holocene seawater, whereas Group 3 salinized samples were probably related to the remnant palaeoseawater of the Late Pleistocene. Group 2 samples had low salinity (TDS < 1 g/L) and undetectable Br− concentrations, which were probably recharged during a colder period and without evidence of seawater involvement. The salinized porewater was likely diluted by freshwater, as evidenced by its depleted isotopes and low salinity relative to standard seawater. The ionic ratios and ionic deltas indicate that considerable water-rock interactions (e.g., cation exchange and mineral weathering) also accounted for the hydrochemical constituents of porewaters, and cation exchange seems to be more noticeable at low salinity.

We elaborate the need for a quality-controlled chemical speciation model for seawater and related natural waters, work which forms the major focus of SCOR Working Group 145. Model development is based on Pitzer equations for the seawater electrolyte and trace components. These equations can be used to calculate activities of dissolved ions and molecules and, in combination with thermodynamic equilibrium constants, chemical speciation. The major tasks to be addressed are ensuring internal consistency of the Pitzer model parameters (expressing the interactions between pairs and triplets of species, which ultimately determines the calculated activities), assessing uncertainties, and identifying important data gaps that should be addressed by new measurements. It is recognised that natural organic matter plays an important role in many aquatic ecosystems, and options for including this material in a Pitzer-based model are discussed. The process of model development begins with the core components which include the seawater electrolyte and the weak acids controlling pH. This core model can then be expanded by incorporating additional chemical components, changing the standard seawater composition and/or broadening the range of temperature and pressure, without compromising its validity. Seven important areas of application are identified: open ocean acidification; micro-nutrient biogeochemistry and geochemical tracers; micro-nutrient behaviour in laboratory studies; water quality in coastal and estuarine waters; cycling of nutrients and trace metals in pore waters; chemical equilibria in hydrothermal systems; brines and salt lakes.

Thermodynamic simulation of the system living matter (algae, zooplankton, or green plants) + mineral matter (25% carbonates + 75% clay minerals) + standard seawater at temperatures and pressure corresponding to diagenesis indicates that kerogen can be synthesized, together with hydrocarbons and carbon dioxide, in the reaction mix. The removal of CO 2 (g) and N 2 (g) from the system is favorable for the reaction Δ 1 C 292 H 288 O 12 (s; H/C = 0.99, O/C = 0.041) → Δ 2 C 128 H 68 O 7 (s; H/C = 0.53, O/C = 0.055) + x СH 4 (aq) + y CO 2 (aq) + z H 2 O, whose constant and stoichiometric coefficients were calculated based on the simulation results. It is demonstrated that a pressure increase is favorable, while a temperature increase is not, for the procedure of this reaction at P-T parameters of diagenesis: log K =–567 (20°C, 35 bar), 1170 (20°C, 200 bar),–1530 (20°C, 60 bar), and +1030 (20°C, 600 bar).

An updated batch-to-batch difference table of IAPSO standard seawater (SSW) up to P145 is proposed. The batch-to-batch difference table is based on several recent SSW comparison experiments, including the experiments conducted independently at the Japan Agency for Marine-Earth Science and Technology (JAMSTEC) and Woods Hole Institute of Oceanography (WHOI) at about the same time using the same procedure. Proposed batch-to-batch differences range from 1.2 × 10−3 to −1.9 × 10−3 with reference to the average of those from P91 to P102. Batch-to-batch differences from P29 to P145 with reference to the recent batches and this average over every 5 years since 1960 are also presented, together with standard deviation. This reveals that inconsistency among batches has improved since 1980s. In particular, the standard deviation was 0.3 × 10−3 in this decade, which is about one-half the value reported previously and almost equal to the modern measurement precision (0.2 × 10−3) and is within-batch difference (<0.3 × 10−3). Proposed batch-to-batch differences were applied to the observational results of the WOCE hydrographic onetime section (WHP onetime) in the Indian Ocean. Average absolute salinity differences at 14 crossover points in the Indian Ocean were slightly larger, from 1.2 × 10−3 to 1.5 × 10−3, when the batch-to-batch difference table was applied; however, when results from the Indian, Pacific, and Atlantic Oceans were combined, application of the batch-to-batch difference table yielded statistically acceptable salinity differences. The table was also applied to WHP sections P1 and P17 (revisited about 10 years after the original observations during the WOCE period) and sections I1, I7, and I8 (visited twice by different research vessels in the same year). In all cases, the table corrected unrealistically large salinity changes in space and time. The results suggest that the application of the batch-to-batch table to well-controlled salinity data such as WOCE datasets would be effective in making the datasets more consistent in space and time.