Dissolved inorganic nitrogen is present in seawater both as nitrite, nitrate and ammonium. As a complement to the overall assessment of nutrient status, detailed information on the distribution of different species must be obtained.

Monitoring of nutrients in seawater is carried out to identify and quantify the amount of nutrients, which may cause eutrophication. The aim is to provide spatiotemporal information for detection of short-term status and long-term trends and to ensure that the data is comparable for the HELCOM core indicator ‘Dissolved inorganic nitrogen‘. The indicator description, including its monitoring requirements, is given in the HELCOM core indicator web site: http://helcom.fi/baltic-sea-trends/indicators/nitrogen-din.

Guidelines for sampling and determination of ammonium (3955)

Hydrogen sulphide is a poisonous gas that readily dissolves in water. The sulphide is formed in stagnant waters, where the oxygen has been consumed by bacteria oxidizing organic matter to carbon dioxide, water, and inorganic ions. Sulphate-reducing bacteria then use the oxygen bound in sulphate ions as an electron acceptor while reducing the sulphate ions to sulphide. No higher life forms can exist in water containing hydrogen sulphide, and these areas are thus turned into oceanic deserts. Hydrogen sulphide in a water sample is easily detected by its characteristic smell, even at concentrations lower than those measurable with the method below.

Monitoring of dissolved oxygen and hydrogen sulphide provide information of an indirect effect of eutrophication. The purpose of the monitoring is to map the spatial distribution of concentrations of dissolved oxygen and hydrogen sulphide, with the aim to be able to assess the status of the seafloor and the waters above and to ensure that the data is comparable for the HELCOM pre-core indicator ‘Shallowwater oxygen’ and core indicator ‘Oxygen debt’. The indicator descriptions, including their monitoring requirements, are given in the HELCOM core indicator web site: http://helcom.fi/baltic-seatrends/indicators/oxygen.

Guidelines for sampling and determination of hydrogen sulphide (H2S) in Seawater (4082)

Dissolved inorganic nitrogen is present in seawater both as nitrite, nitrate and ammonium. As a complement to the overall assessment of nutrient status, detailed information on the distribution of different species must be obtained.

Monitoring of nutrients in seawater is carried out to identify and quantify the amount of nutrients, which may cause eutrophication. The aim is to provide spatiotemporal information for detection of short-term status and long-term trends and to ensure that the data is comparable for the HELCOM core indicator ‘Dissolved inorganic nitrogen‘. The indicator description, including its monitoring requirements, is given in the HELCOM core indicator web site: http://helcom.fi/baltic-sea-trends/indicators/nitrogen-din.

Guidelines for sampling and determination of nitrate (3606)

Dissolved inorganic nitrogen is present in seawater both as nitrite, nitrate and ammonium. As a complement to the overall assessment of nutrient status, detailed information on the distribution of different species must be obtained.

Monitoring of nutrients in seawater is carried out to identify and quantify the amount of nutrients, which may cause eutrophication. The aim is to provide spatiotemporal information for detection of short-term status and long-term trends and to ensure that the data is comparable for the HELCOM core indicator ‘Dissolved inorganic nitrogen‘. The indicator description, including its monitoring requirements, is given in the HELCOM core indicator web site: http://helcom.fi/baltic-sea-trends/indicators/nitrogen-din.

Guidelines for sampling and determination of nitrite (3509)

Since ocean acidification is a growing concern, monitoring of pH is necessary for studies of acidification and its effects on the carbonate buffer system. As many important biological processes are likely to be affected by rapid changes in pH, it is important to include accurate determination of pH among monitoring parameters. pH is operationally defined, and a number of pH scales are used in environmental monitoring. The NBS (National Bureau of Standards) scale is suitable for waters of low ionic strength, and used for freshwater monitoring. The total hydrogen ion scale is often used for pH determinations in oceanic waters. The salinity gradient from the Bothnian Bay to Skagerrak, or from surface to deep water in the Baltic Proper, makes it difficult to select a pH scale that would be suitable for the entire Baltic area. pH is also used in marine environmental monitoring as a co-factor in measurements of primary production..

Guidelines for sampling and determination of pH in seawater (3955)

Monitoring of nutrients in seawater is carried out to identify and quantify the amount of nutrients, which may cause eutrophication. The aim is to provide spatiotemporal information for detection of short-term status and long-term trends and to ensure that the data is comparable for the HELCOM core indicator ‘Dissolved inorganic phosphorus‘. The indicator description, including its monitoring requirements, is given in the HELCOM core indicator web site: http://helcom.fi/baltic-sea-trends/indicators/phosphorus-dip.

Guidelines for sampling and determination of phosphate (3667)

Silicate is introduced to the Baltic Sea as a result of natural geological processes, as opposed to nitrogen and phosphorus, which levels are affected by human activities. Although it is not listed among the HELCOM Core Indicators, silicate is still biologically significant. Since diatoms are dependent of dissolved silicate for growth, monitoring of silicate is essential for evaluation and modelling of nutrient status, and assessment of conditions for phytoplankton growth.

Guidelines for sampling and determination of silicate (3761)

Although not listed among HELCOM Core Indicators, total alkalinity should be monitored to provide information of alterations in the carbonate buffer system, which may be induced by changing weathering processes on the continents or internal processes in the Baltic Sea. Although alkalinity is not affected by increasing atmospheric CO2, it controls the pH at a given atmospheric CO2 level. Hence its long-term changes are interacting with ocean acidification induced by the dissolution of anthropogenic CO2.

The aim of monitoring is to identify spatial variations and temporal trends in total alkalinity.

Guidelines for sampling and determination of total alkalinity (3705)

Total nitrogen includes all organic and inorganic forms of nitrogen, dissolved as well as suspended or particulate. The results are an estimation of the total amount of nitrogen, not only the dissolved bioavailable fraction.

Monitoring of nutrients in seawater is carried out to identify and quantify the amount of nutrients, which may cause eutrophication. The aim is to provide spatiotemporal information for detection of short-term status and long-term trends and to ensure that the data is comparable for the HELCOM core indicator ‘Dissolved inorganic nitrogen‘. The indicator description, including its monitoring requirements, is given in the HELCOM core indicator web site: http://helcom.fi/baltic-sea-trends/indicators/nitrogen-din.

Guidelines for sampling and determination of total nitrogen (3657)

While determination of dissolved phosphate gives information on the bioavailable pool of phosphorus, an assessment of the total amount of phosphorus is also essential.

Total phosphorus includes all organic and inorganic forms of phosphorus present in seawater, particulate as well as dissolved. The dissolved organic phosphorus is also partly bioavailable, mainly when phosphate is exhausted. Also the particulate fraction can be used in part.

Monitoring of nutrients in seawater is carried out to identify and quantify the amount of nutrients, which may cause eutrophication. The aim is to provide spatiotemporal information for detection of short-term status and long-term trends and to ensure that the data is comparable for the HELCOM core indicator ‘Dissolved inorganic phosphorus‘. The indicator description, including its monitoring requirements, is given in the HELCOM core indicator web site: http://helcom.fi/baltic-sea-trends/indicators/phosphorus-dip.

Guidelines for sampling and determination of total phosphorus (3669)

Water transparency serves as an index forthe trophic state of a water body. It reflects eutrophication through changes in the phytoplankton abundance; increase in the ambient nutrient status in the water leads to higher phytoplankton biomass that diminishes the propagation of light in the water.

Water transparency is approached by Secchi depth (Cialdi and Secchi 1865, Whipple 1899). Secchi depth is influenced by dissolved and/or colloidal inorganic and organic substances as well as total suspended solids and resident seston. It is thus affected by substances unrelated to eutrophication as well. This source of error has to be taken into consideration whenever eutrophication state is assessed using Secchi depth in the Baltic Sea that is optically classified as a Case II water body (Morel and Prieur 1977), i.e., the body where concentrations of colour producing substances (e.g. phytoplankton, inorganic particles and CDOM) vary independently from each other. Those Secchi depth estimations should be treated with special caution that are collected in the sub-basins possessing high absorption by chromophoric dissolved organic matter (the Gulf of Riga, the Gulf of Bothnia).

Secchi depth relates to primary production by being a proxy for the thickness of the euphotic zone wherein the large bulk of the gross production takes place. In principle, the euphotic depth is twice Secchi depth, but this relation varies largely in practice (French et al. 1982).

Guidelines for monitoring of water transparency (Secchi depth) (4048)

Increase in phytoplankton biomass is a direct consequence of advancing eutrophication. For monitoring purposes, phytoplankton biomass is estimated by chlorophyll a (Chl a) concentration.

The amount of Chl a is not a direct proxy for phytoplankton biomass because of a highly variable ratio of cellular carbon to Chl a in phytoplankton (Geider 1987). Phytoplankton biomass, except for picoplankton, is more accurately assessed by quantitative taxonomical analysis. It is, however, laborious and thus provides with a smaller amount of data than the Chl a method, which lowers the status confidence of any taxonomybased indicator. Regardless of its shortcomings, the Chl a method ‒ being easy to sample and fast to analyze ‒ is the method of choice for environmental studies.

The scope of this guideline is the determination of Chl a concentration; measured from water samples using wet analytics as well as estimated from in vivo Chl a fluorescence recordings.

Guidelines for measuring chlorophyll a (4048)

Salinity measurements based on electrical conductivity have since the 1960s replaced measurements of chlorinity. The Practical Salinity Scale of 1978 (PSS-78) presently used, has been defined to maintain a continuity with older scales and methods. The scale is based on conductivity of a reference solution prepared from potassium chloride. Practical Salinity (SP)is calculated from the ratio of conductivity between sample and reference solution.

Since the scale is based on a ratio, no unit is assigned to it. Despite this, salinity data are sometimes presented with the units ‰ or psu. The equations used in calculation of Practical Salinity from conductivity are valid for practical salinity ranging from 2 to 42.

A new standard for the properties of seawater was introduced in 2010; the thermodynamic equation of seawater 2010 (TEOS-10). This standard also includes a new scale, called the Absolute Salinity scale. Absolute Salinity (SA) is expressed as a mass fraction, in grams per kilogram of solution. While Absolute Salinity is the variable needed to calculate density and other properties of seawater, Practical Salinity is still the variable measured, reported and archived in marine environmental monitoring.

Temperature sensors are calibrated to the ITS 90scale.

Guidelines for determination of salinity and temperature using CTD (3931)

These guidelines concentrate on the sampling and extraction of lipophilic persistent organic pollutants from seawater and also address special aspects of the sampling matrix. Those pollutants comprise the group of polycyclic aromatic hydrocarbons (PAHs) and chlorinated hydrocarbons (e.g., HCH, HCB, DDT group, chlorinated biphenyls (PCBs)).

Usually, similar analytical methods are used for the determination of lipophilic pollutants in extracts from water samples and from sediments. Therefore, it is meaningful to harmonize analytical procedures and to refer to the respective references. (see 7. CHROMATOGRAPHIC DETERMINATION)

However, it should be taken into consideration (e.g., for calibration) that the relative concentrations of the individual pollutants are different in water and sediment samples which is basically attributed to the compound’s polarity and, thus, their octanol/water partition coefficient (log Kow; Kow = Concentration in octanol phase / Concentration in aqueous phase). Thus, in water samples the more hydrophilic compounds with log Kow values of 3 to 4 predominate (e.g., 2- and 3-ring aromatics and HCH isomers), while in sediments and biota pollutants with log Kow values >5 are enriched (4- to 6-ring aromatics, DDT group, PCBs).

Guidelines for determination of POPs in seawater (3912)

This Technical note provides advice on the analysis of polycyclic aromatic hydrocarbons (PAH) in total marine sediments, sieved fractions, and suspended particulate matter. The analysis of PAH compounds in sediments basically includes extraction with organic solvents, clean-up, and separation through high performance liquid chromatography (HPLC) with ultraviolet (UV) or fluorescence detection or gas chromatographic separation (GC) with flame ionization (FID) or mass spectrometric (MS) detection (Kassim & Barcelo, 2009, 1989; Wise et al., 1995).

All steps of the procedure are susceptible to insufficient recovery and contamination. Quality control measures are recommended in order to regularly monitor the performance of the method. These guidelines are intended to encourage and assist analytical chemists to critically review their methods and to improve their procedures and quality assurance measures, if necessary.

These guidelines are not intended as complete laboratory manual. If necessary, guidance should be sought from specialized laboratories. Laboratories should demonstrate validity of each methodological step.

Guidelines for the determination of PAH in sediment (4201)

These guidelines are based on the review from Smedes and de Boer (1994, 1998) and Eljarrat and Barceló (2009).
The analysis of chlorinated hydrocarbons in sediments generally involves extraction with organic solvents, clean-up, removal of sulphur, column fractionation and gas chromatographic separation, mostly with electron capture or mass-spectrometric detection.

All steps of the procedure are susceptible to insufficient recovery and contamination. Quality control measures are recommended in order to regularly monitor the performance of the method. These guidelines are intended to encourage and assist analytical chemists to critically review their methods and to improve their procedures and quality assurance measures, if necessary.

These guidelines can be applied for the determination of several types of chlorinated hydrocarbons, e.g., chlorinated biphenyls (CB), chlorobenzenes, DDT and its metabolites and hexachlorocyclohexanes. It should be noted that these guidelines do not cover the determination of non-ortho substituted CB. Due to the low concentrations of non-ortho CB in sediments comparing to those of other CB, their determination requires an additional separation and concentration step similar to the analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F).

Guidelines on the determination of chlorinated hydrocarbons in sediment (HELCOM) (4116)

FAO, IOC, IAEA, UNEP, 1992

This document provides guidance on the design of such programmes and is intended for scientists who are responsible for marine pollution monitoring programmes. It is particurlary aimed at programmes which fall under the auspices of the UNEP, IOC and FAO

The guidelines presented in this report cover the following aspects of marine pollution monitoring programmes:
- aims
- pilot studies
- criteria for the selection of contaminants, organisms and locations to be studied
- size of sample
- frequency of sampling operations
- tissue selection.

Although an important component of these programmes is the analysis of contaminants in samples, this matter will not be addressed in detail in this document sinceother UNEP Reference Methods For Marine Pollution Studies cover this topic. Readers of this document are therefore advised to have the relevant analytical documents to hand (see UNEP/IOC/IAEA 1990); particularly "Contaminant monitoring programmes using marine organisms: Quality Assurance and Good Laboratory Practice" Reference Method No 57, since this deals with all aspects of work which influence the quality of data.

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WP9, UPGRADE BLACK SEA SCIENTIFIC NETWORK, 2011

The document describes procedures that make extensive use of specific data quality flags, processing/archive formats and tools that developed in the framework of several research projects. In order to standardize the QC procedures and ensure data reability, consistency and interoperability with other systems, Upgrade-BSS project adopts the SeaDataNet standards, vocabularies, exchange formats, and tools for quality control.

The guidelines include the quality control procedures in real time and delayed mode which are carried out by the NODCs and research Institutes for vertical profiles, time series, trajectories and wave data. They do not include information for field data collection and laboratory methods.

The procedures are intended to cover the physical (temperature and salinity) and chemical (oxygen and nutrients) oceanographic data but there are obvious generalizations that can be made to other parameters measured from the same instruments.

 

 

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By Stuart L Simpson, Graeme E Batley, Anthony A Chariton, Jenny L Stauber, Catherine K King, John C Chapman, Ross V Hyne, Sharyn A Gale, Anthony C Roach, William A Maher, 2005

This Handbook discusses the approaches and methods that are recommended for sediment quality assessment that build the ANZECC/ARMCANZ tiered assessment and the integrated assessment philosophy. These involve the use of multiple lines of evidence (LOE), and considerations of howthese can be integrated in weight-of-evidence (WOE) frameworks to be used in decision- making.

The Handbook summarises the latest science, and provides information to guide future investigations. Since the majority of Australia's sediment contamination concerns are with urban harbours that are estuarine and marine systems, guidance is largely restricted to these systems. While many of priciples will be equally applicable to freshwater systems, no guidance is provided for toxicity test and ecological assessment procedures for freshwater systems

 

 

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By Jesper H. Andersen • Philip Axe • Hermanni Backer • Jacob Carstensen • Ulrich Claussen • Vivi Fleming-Lehtinen • Marko Ja¨rvinen • Hermanni Kaartokallio • Seppo Knuuttila • Samuli Korpinen • Aiste Kubiliute • Maria Laamanen • Elzbieta Lysiak-Pastuszak • Georg Martin • Ciara´n Murray • Flemming Møhlenberg • Gu¨nther Nausch • Alf Norkko • Anna Villnas, 2 July 2010

The eutrophication status of the entire Baltic Sea is classified using a multi-metric indicatorbased assessment tool. A total of 189 areas are assessed using indicators where information on reference conditions (RefCon), and acceptable deviation (AcDev) from reference condition could be combined with national monitoring data from the period 2001–2006. Most areas (176) are classified as ‘affected by eutrophication’ and only two open water areas and 11 coastal areas are classified as ‘unaffected by eutrophication’. The classification is made by application of the recently developed HELCOM Eutrophication Assessment Tool (HEAT), which is described in this paper.

The use of harmonized assessment principles and the HEAT tool allows for direct comparisons between different parts of the Baltic Sea despite variations in monitoring activities. The impaired status of 176 areas is directly related to nutrient enrichment and elevated loads from upstream catchments. Baltic Sea States have implemented nutrient management strategies since years which have reduced nutrient inputs. However, eutrophication is still a major problem for large parts of the Baltic Sea. The 2007 Baltic Sea Action Plan is projected to further reduce nutrient inputs aiming for a Baltic Sea unaffected by eutrophication by 2021.

 

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