Feasibility study of preparation and certification of reference materials for nitrogen dioxide and sulfur dioxide in diffusive samplers

This paper presents the results of a feasability study for the preparation and certification of reference materials (RMs) for nitrogen dioxide (NO(2)) and sulfur dioxide (SO(2)) in diffusive samplers. RMs for NO(2) were prepared by exposure to gas mixtures in a chamber while the RMs for SO(2) were prepared by liquid spiking. Certification of RMs for NO(2) was found feasible with a certified uncertainty of 5.8% and a proposed shelf life of 5 years. The uncertainty was calculated with contribution from the homogeneity of preparation, stability and transport of the CRMs and from an external verification of the certified value. To reach 5.8% of uncertainty, the contribution of the differences between the results of analysis by ion chromatography and colorimetry must be eliminated. It is proposed to solve this by pre-extracting the samplers with water before analysis. The results of this study indicate that the samplers are stable for at least two years before and after exposure when stored in a refrigerator. By contrast, the certification of RMs for SO(2) was found to not be feasible due to instability problems. This instability was attributed to reaction of sulfate on the walls of the samplers. Alternatively, the preparation of RMs by simultaneous exposure to SO(2) and NO(2) has been tested. Satisfying homogeneities has been reached both for NO(2) and SO(2).     

Reference materials for the monitoring of the aquatic environment--a review with special emphasis on organic priority pollutants

During recent years, the awareness of quality assurance and quality control in environmental analyses has constantly increased, especially due to the implementation of new guidelines and regulations at both the national and international level. Achieving comparable results by using certified reference materials is one of the primary concerns of the scientific community. As a result, there is a growing demand for certified reference materials to cover different matrices and pollutants. Moreover, these CRMs should be in close relationship to the determinants and target concentrations required by environmental bodies and European Directives as well. Supplementary information to this paper presents an inventory of reference materials available on the market from different suppliers against the priority pollutants listed in the Water Framework Directive. These CRMs cover matrices such as water, sediment and biota. The use of CRMs in relationship to appropriate analytical methods and relevant determinants is discussed and the need for matrix-CRMs, particularly for organic pollutants is emphasised. The use of proficiency testing schemes as an alternative for the lack of appropriate CRMs and future trends in the production of CRMs within the BCR framework are also discussed.     

河口混合区划定及营养盐标准限值构建

河口是河流和海洋生态系统的过渡带,目前中国缺乏河口区划界和水质评价标准,河口区及其附近海域环境质量评价直接使用《海水水质标准》(GB 3097—1997)对标评价的方式,评价结果往往与实际不符,对河口地区开发建设和管理保护不利。笔者系统分析了中国河口区划分及水质评价的现状和存在问题,以北部湾主要入海河口钦州湾为例比较了河口区营养盐背景值与海洋营养盐背景值,两者差异显著,认为使用《海水水质标准》(GB 3097—1997)对河口区进行评价不能很好地反映环境质量。因此依据现行的《地表水环境质量标准》(GB 3838—2002)、《海水水质标准》(GB 3097—1997)和《近岸海域环境功能区管理办法》,提出使用盐度等数据探讨河口混合区划定及建立河口混合区水质营养盐标准限值的方法。在钦州湾的应用案例中,河口混合区的划定和河口区营养盐标准限值确定,都具有科学性和可操作性。使用河口混合区营养盐标准进行评价的结果比直接使用《海水水质标准》(GB 3097—1997)评价能更准确地反映环境质量,可为河口区划界及水质评价提供方法参考。     

基于反距权重插值的入海河口水环境研究

对某入海河口在春季和夏季进行2次水体环境因子(TP、TN、COD、Chla、SS)监测,利用Arc Map扩展模块中反距离权重插值模型,对各监测值分别进行插值分析。通过插值结果,对营养盐、Chla、COD和SS在时间和空间上的差异进行探讨,揭示了入海河口水体环境因子在季节差异和流域分布上的独有特点。     

Investigating the spatial distribution of phototrophic picoplankton in a tropical estuary

We sampled extensively (29 stations) at the Klang estuarine system over a 3-day scientific expedition. We measured physical and chemical variables (temperature, salinity, dissolved oxygen, total suspended solids, dissolved inorganic nutrients) and related them to the spatial distribution of phototrophic picoplankton (Ppico). Multivariate analysis of variance of the physicochemical variables showed the heterogeneity of the Klang estuarine system where the stations at each transect were significantly different (Rao’s F _{18, 36}?=?8.401, p?<?0.001). Correlation analyses also showed that variables related to Ppico abundance and growth were mutually exclusive. Distribution of Ppico was best explained by the physical mixing between freshwater and seawater whereas Ppico growth was correlated with temperature.     

The role and distribution of total suspended solids in the macrotidal coastal waters of Korea

Spatial and temporal distribution patterns of total suspended solids (TSS) in the shallow and macrotidal regions of the Korean peninsula indicated there were significant changes in TSS concentrations. These were seasonally influenced by the wind, river input and tidal cycle. There were high TSS values at estuarine and river mouth stations and during low tide due to the re-suspension of bottom sediment by strong wind action during winter months, in addition the land input through rivers and strong tidal current during ebbing. Monthly mean values of TSS significantly correlated with wind speed and nitrate concentration (p < 0.01). This indicated that the resuspension of surface sediment was a more important source of TSS than the river input, and that nitrate was introduced into the water column during the resuspension process. TSS were seven times higher at low tide than in high tide. Light penetration was significantly inhibited by TSS; as >98% of incident light was absorbed within 2 m and zero photosynthetically active radiation (PAR) under 2 m in the estuarine stations during winter. Removal of heavy metals and nutrients by TSS in the water column was evident. Over 80% of the initial concentration of nutrients was removed within 10 min under various concentrations of TSS and also TSS contained significantly higher concentration of heavy metals than surface sediment. The concentration levels of nutrients and chemical oxygen demand in the west coast were comparable with the East and South Sea, even the major rivers in the Korean peninsula flow into the West Sea with major pollutant loadings into the coastal areas. High concentration of TSS is likely to contribute to the removal process of these pollutants, resulting in relatively lower levels of nutrients and organic materials in these coastal waters.     

新标准方法实施后水中石油类检测实验室能力验证结果比对研究

为推进国际履约进程,我国自2019年1月1日起停止实验室用途使用四氯化碳,原针对水中石油类的分析方法《水质石油类和动植物油类的测定红外分光光度法》(HJ 637—2012)随之失效,新分析方法则在2018年10月正式发布。随着新分析方法的发布实施,有必要考察实验室采用新方法分析水中石油类的能力。通过汇总两次能力验证计划的统计结果,分析了实验室采用两种新方法分析水中石油类的能力。结果显示:采用紫外分光光度法(HJ 970—2018)和红外分光光度法(HJ 637—2018)测定水中石油类能力验证参加实验室的满意率分别为79.1%和86.6%,分别低于和高于新方法发布之前水中石油类检测能力验证参加实验室的满意率。实验室在操作时的样品空白、正己烷透光率以及器皿污染控制等因素对检测结果的影响较大。目前市场上用于水质检测的石油类标准样品的来源较广泛,原料来源的不同可能导致标准量值存在差异,从而导致不同实验室的分析结果偏差较大。     

Different hydrodynamic processes regulated on water quality (nutrients,dissolved oxygen,and phytoplankton biomass) in three contrasting waters of Hong Kong

The subtropical Hong Kong (HK) waters are located at the eastern side of the Pearl River Estuary. Monthly changes of water quality, including nutrients, dissolved oxygen (DO), and phytoplankton biomass (Chl-a) were routinely investigated in 2003 by the Hong Kong Environmental Protection Department in three contrasting waters of HK with different prevailing hydrodynamic processes. The western, eastern, and southern waters were mainly dominated by nutrient-replete Pearl River discharge, the nutrient-poor coastal/shelf oceanic waters, and mixtures of estuarine and coastal seawater and sewage effluent of Hong Kong, respectively. Acting in response, the water quality in these three contrasting areas showed apparently spatial–temporal variation pattern. Nutrients usually decreased along western waters to eastern waters. In the dry season, the water column was strongly mixed by monsoon winds and tidal currents, which resulted in relatively low Chl-a (<5 μg l^?1) and high bottom DO (>4 mg l^?1), suggesting that mixing enhanced the buffering capacity of eutrophication in HK waters. However, in the wet season, surface Chl-a was generally >10 μg l^?1 in southern waters in summer due to halocline and thermohaline stratification, adequate nutrients, and light availability. Although summer hypoxia (DO <2 mg l^?1) was episodically observed near sewage effluent site and in southern waters induced by vertical stratification, the eutrophication impacts in HK waters were not as severe as expected owing to P limitation and short water residence time in the wet season.     

Linking phosphorus export and hydrologic modeling: a case study in Central Italy

Soil erosion is an open topic, not only because soil fertility is lost, but also because nutrients are spilled into water bodies, thereby causing pollution. Research carried out in this field has amply described this process, but the interaction between these factors is complex and experimental research is needed to understand the production of loads of nutrients for different land uses. This paper describes a long-term monitoring case study using high-resolution rainfall data and runoff samples, carried out in the Lake Vico basin (Central Italy) to determine the phosphorus (P) export during erosive rainfall events. State of the art GIS-based basin characterization and advanced rainfall-runoff models are employed in order to describe the relationship between nutrient export and rainfall or runoff time distribution. Results show that the phosphorus export is strongly related to such time distributions, and less to the cumulative amount of rainfall or runoff.     

Assessing the influence of nutrient reduction on water quality using a three-dimensional model: case study in a tidal estuarine system

A coupled three-dimensional hydrodynamic and water quality model has been developed and applied to the Danshuei River estuarine system and adjacent coastal sea. The water quality model considers various species of nitrogen, phosphorus, organic carbon, and phytoplankton as well as dissolved oxygen and is driven by a three-dimensional hydrodynamic model. The hydrodynamic and water quality models were validated with observations of water surface elevation, velocity, salinity distribution, and water quality parameters. Statistical error analysis shows that predictions of hydrodynamics, salinity, dissolved oxygen, and nutrients from the model simulation quantitatively agreed with the observed data. The validated model was then applied to predict water quality conditions as a result of a reduction in nutrient loadings based on different engineering strategies. The simulated results revealed that the dissolved oxygen concentration would increase significantly and would be higher than 2 mg/L in the main stream and in three tributaries to meet the minimum statutory requirement for dissolved oxygen. Active estuarine management focused on the reduction of anthropogenic nutrient loads is needed for improvement in water quality.     

Seasonal effects on the air-water carbon dioxide exchange in the Hooghly estuary,NE coast of Bay of Bengal,India

Monthly variation of CO2 fugacity (fCO2) in surface water and related atmospheric exchanges were measured in the Hooghly estuary which is one of the most important estuaries, since it is fed by one of the world's largest rivers, the Ganges with a flow of 15,646 m3 s-1 (1.6% of the world's combined river flow). Carbon dioxide fluxes averaged over the entire estuary are in the range of -2.78 to 84.4 mmol m-2 d-1. This estuary acts as a sink for CO2 during monsoon months and seasonal variation of its flux is controlled by dilution of seawater by river water. Since the solubility of CO2 and the disassociation of carbonic acid in estuarine water are controlled by temperature and salinity, the observed variations of CO2 fluxes are compared with those predicted from seasonal changes in temperature, salinity and the ratio of gross primary production to community respiration using empirical equations with an explained variability of 55%.     

Physical and chemical characteristics of water from the hydrographic basin of the Poxim River, Sergipe State, Brazil

The Poxim River is one of Sergipe State’s major waterways. It supplies water to the State capital, Aracaju, but is threatened by urban and agricultural developments that compromise both the quantity and the quality of the water. This has direct impacts on the daily lives of the region’s population. In this work, a multivariate analytical approach was used to investigate the physical and chemical characteristics of the water in the river basin. Four sampling campaigns were undertaken, in November 2005, and in February, May, and September 2006, at 15 sites distributed along the Poxim. The parameters analyzed were conductivity, turbidity, color, total dissolved solids, dissolved oxygen, alkalinity, hardness, chlorophyll-a, and nutrients (total phosphorus, dissolved orthophosphate, nitrite, nitrate, ammoniacal nitrogen, and total nitrogen). Dissolved oxygen contents were very low in the Poxim-Açu River (1.0–2.8), the Poxim River (1.6–4.6), and the estuarine region (1.7–5.1), due to the dumping of wastes and discharges of domestic and industrial effluents containing organic matter into fluvial and estuarine regions of the Poxim. Factor analysis identified five components that were indicative of the quality of the water, and that explained 81.73 % of the total variance.     

The New Danish Stream Monitoring Programme (Novana) – Preparing Monitoring Activities For The Water Framework Directive Era

Denmark has a long tradition of monitoring the aquatic environment. Previous monitoring has mainly focused on loss of nutrients and subsequent impacts on the biological structure in lakes and coastal areas. However, as part of the third Action Plan for the Aquatic Environment more emphasis has been put on stream ecology. The present paper describes background, strategy and content of the new NOVANA stream programme, which will run for the period 2004–2009. The new programme will encompass more than 800 stations covering all stream types in Denmark and monitoring will include three biological quality elements (macrophytes, macroinvertebrates and fish) as well as physico-chemical features and hydromorphological elements. In addition, the new programme integrates monitoring of elements both in the stream itself and in the riparian zone. Compliance with important European Commission Directives such as the Water Framework Directive and the Habitat Directive is discussed.     

2019年连云港近岸海域水质环境分析与综合评价

于2019年春、夏、秋季对连云港近岸海域海水中营养盐、重金属等共19项指标进行3个航次采样监测。依照海水水质评价标准统计分析站点达标率,采用有机污染物指数法和富营养化指数法,对调查海域海水有机污染、营养水平等进行综合评价。结果表明:2019年连云港市海域站位全年达标率为86.4%,达标面积为6543 km²,占管辖海域面积的98.0%,水质质量较往年有所好转,主要超标物为无机氮、活性磷酸盐。调查海域海水的有机污染和富营养化程度均处于良好状况,近岸海水水质总体上要劣于远岸水质,且随季节的更替呈现波动性变化。     

Depositional behaviour of C-org, N, P and K in the surface sediments of two shallow water bodies in a tropical coast, India

The present paper deals with the distribution of sediment and sediment-bound nutrients in two important coastal lagoons of southern Kerala such as the Ashtamudi Estuarine Lagoon in the Kollam district and the Kadinamkulam Lagoon in the Thiruvananthapuram district. Among the two lagoons, the former is coast perpendicular, and the latter is coast parallel. An analysis of the textural characteristics reveals that, in both lagoons, the estuarine mouth and areas close to it are dominated by sand and sand-rich sediment species, indicating a high-energy depositional regime prevailing the region. On the other hand, the silt and clay dominant arms are almost sheltered and enjoy a low-energy depositional environment. The nutrient and organic carbon contents in the sheltered areas are significantly higher than the most dynamic high-energy estuarine mouth regions. This peculiar behaviour of these coastal water bodies has to be given adequate importance while laying down strategies for the conservation and management of these fragile aquatic systems in the south-western coast of India in particular and tropical coasts of the world in general.     

Inter-relations between biological and physicochemical factors in a database for a shallow estuarine system

This paper examines data obtained since 1976 in Peel Inlet and the Harvey Estuary, a shallow estuarine system in Western Australia, which has nuisance growths of macroalgae and seasonal blooms of the cyanobacterium (blue-green alga)Nodularia spumigena. Data collected at the same sites at weekly or fortnightly intervals include phytoplankton (chlorophylla), water nutrients (nitrogen and phosphorus), salinity, temperature and light penetration. Seasonally, the biomass of macroalgae has been measured at a number of sites and used to estimate total biomass.The data are characterised by large season-to-season differences, attributable to the seasonality and volume of river flow. The information has been used to relate the magnitude of summer blue-green algal blooms to the winter loading of phosphorus from the surrounding catchment, and the magnitude of macroalgal biomass to light penetration through the water column.     

Chemical speciation of inorganic pollutants in river–estuary–sea water systems

Monitoring studies and thermodynamic modeling were used to reveal the changes of inorganic chemical species of some water pollutants (nutrients and trace metals such as Fe, Mn, Zn, Cu, Cd and Pb) inthe river-estuary-sea water system. The case studies were two rivers, Kamchiya and Ropotamo, representing part of the Bulgarian Black Sea water catchment area, and having different flow characteristics. There were no major differences in inorganic chemical species of the two river systems. NO3(-) and NO2(-) chemical species showed no changes along the river-estuary-sea water system. Concerning phosphates six different species were calculated and differences between the three parts of the systems were established. The HPO4(2-) and H2PO4(-) species were found to be dominant in river waters. The H2PO4(-) species quickly decreased at the expense of HPO4(2-) and Ca, Mg and Na phosphate complexes in estuary and seawater. Trace metals showed a great variety of chemical species. Fe(OH)2(+) species prevailed in river waters, and Fe(OH)3(0) species--in sea waters. Me2+ and MeCO3(0) (Me = Cu, Pb) and PbHCO3(+) were dominant in river waters, while Cu(CO3)2(2-) and PbCl(-) species appear also in sea waters. Cd2+ species prevailed in river and estuary waters, and CdCln(2-n) (n = 1-3) species, in seawater. Free Zn2+ species predominated in all systems but downstream their percentage decreased at the expense of Zn phosphates, carbonates,sulfates and chlorides complexes. Only free Mn2+ species were dominant along the systems.     

Environmental impact of seawater desalination plants

Enormous amounts of seawater are desalted everyday worldwide. The total world production of fresh water from the sea is about 2621 mgd (9.92 million m³ day^-1 1985 figures). Desalting processes are normally associated with the rejection of high concentration waste brine from the plant itself or from the pretreatment units as well as during the cleaning period. In thermal processes, mainly multistage flash (MSF) thermal pollution occurs. These pollutants increase the seawater temperature, salinity, water current and turbidity. They also harm the marine environment, causing fish to migrate while enhancing the presence of algae, nematods and tiny molluscus. Sometimes micro-elements and toxic materials appear in the discharged brine.This paper will discuss the impact of the effluents from the desalination plants on the seawater environment with particular reference to the Saudi desalination plants, since they account for about 50% of the world desalination capacity.     

Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials

The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union.     

Impact of artificial lagoons on seawater quality: evidence from 7 years of physicochemical seawater monitoring

Seven years (2010–2016) of data on the basic physicochemical properties of seawater, temperature, salinity, dissolved oxygen (DO), nutrients, chlorophyll a (Chl a), and hydrocarbons from two lagoons were used to evaluate the impact of the anthropogenic activities inside the lagoon on the water quality and to explore the relationship of any impact from the lagoons’ design. Statistical analysis shows the modification in water quality inside the lagoon compared to the ambient seawater is particularly evident for nitrate, silicate, and Chl a. The modification is attributed to the extensive boat activities in the lagoons and the limited water exchange between the lagoons and ambient seawater. However, the impact to both lagoons is generally limited to inside the lagoons. The oligotrophic state of the two lagoons was evaluated and it was found that the most marked code violations were found in DIN inside both lagoons. In order to explore the design importance, the water exchange and overall water quality was compared between the two lagoons. This study highlights the importance of an environmental design study before the construction of any lagoon project. Proper design would maintain acceptable water quality inside the lagoons, critical for environmental health and supporting continued recreational activities.