三重四极杆电感耦合等离子体质谱法测定水中痕量磷的方法建立及在新安江水库的应用

建立了三重四极杆电感耦合等离子体质谱法（ICP-MS/MS）测定地表水中痕量总磷、溶解态磷、颗粒态磷的方法，确定了ICP-MS/MS测定水中磷的仪器参数及氧气流量。研究了该方法检测水中磷元素的检出限、精密度、正确度，探索了浊度、色度及砷、铬、硫的存在对ICP-MS/MS测磷的影响。结果表明，采用高纯氧气反应ICP-MS/MS法可对地表水中的各形态痕量磷进行质量浓度检测，该方法的检出限可达0.24 μg/L，磷元素在1.00～1 000 μg/L 质量浓度范围内具有良好的线性，相关系数为0.999 5，加标回收率为 92%～103%。该方法检测速度快，抗浊度、色度及共存元素（砷、铬、硫）干扰的能力强。对新安江水库4个季度的总磷、溶解态磷、颗粒态磷进行测定，结果表明，水库总磷平均质量浓度为10～20 μg/L，ρ（溶解态磷）/ρ（总磷）为42.4%～50.9%。该方法可以满足地表水中痕量磷的快速测定及形态分析。     

漳河上游流域沉积物中磷的空间分布特征及其影响因素

漳河上游地区众多的水利工程改变了流域水循环,同时也影响了河流泥沙和生源物质的循环过程。为揭示人类活动干扰下的沉积物中磷的赋存特征,采用改进后的连续化学萃取法分析了漳河上游沉积物中总磷(TP)和磷形态的空间分布特征及其影响因素。研究结果表明,漳河上游沉积物中的TP含量为405.94~899.98 mg/kg,低于我国其他主要河流,接近我国东部平原湖泊含量水平。漳河上游的TP富集指数(PEI)均值为1.15,表明漳河上游富营养化风险较高。可交换态磷(Ex-P)、铁锰螯合态磷(BD-P)、铁铝氧化态磷(NaOH-P)、钙结合态磷(HCl-P)分别占沉积物中TP含量的1.13%、33.96%、12.99%、35.05%。BD-P和HCl-P是沉积物中主要的磷形态,Ex-P的含量最低,NaOH-P的含量波动最大。漳河上游沉积物中,生物可利用磷(BAP)的含量约占TP含量的38.36%~52.04%,其中,清漳干流的BAP含量明显低于其他河段。清漳源头的水土流失及浊漳河的磷输入对漳河上游BAP含量的贡献较大。统计分析显示,漳河上游表层沉积物中,TP和磷形态的空间分布无显著差异,表明以水利工程建设为代表的强烈人类活动对漳河上游沉积物中磷的空间分布的影响不显著。相关性分析和冗余分析表明,沉积物中的NaOH-P含量与沉积物中黏土和粉土的占比有较高的相关性,BD-P和NaOH-P是控制沉积物中BAP构成的重要因素,Fe含量是沉积物中TP含量的主控因子。     

镇江市金山湖沉积物磷元素分布特征研究

以镇江市金山湖为研究区域，于2019年1月（冬季）和2019年7月（夏季）采集了10个点位的表层沉积物样品，参照欧洲标准测试测量组织建立的沉积物磷形态分析方法（SMT）测定沉积物总磷（TP）、无机磷（IP）、有机磷（OP）、铁/铝-磷（Fe/Al-P）和钙-磷（Ca-P）质量分数，研究金山湖表层沉积物磷元素及其赋存形态的季节分布特征。结果表明，金山湖表层沉积物中TP质量分数在冬、夏季分别为727.39~1 073.70 mg/kg和700.90~1 002.17 mg/kg，处于中等污染水平；金山湖表层沉积物磷以IP为主，IP在TP中的占比在冬、夏季分别为68.58%~88.86%，73.09%~87.21%；除了Fe/Al-P以外，OP作为生物有效磷源，其冬、夏季质量分数分别为69.37~190.93 mg/kg和108.45~210.42 mg/kg；其平均值分别为129.01，160.15 mg/kg。金山湖冬、夏季沉积物各形态磷质量分数所占比例均表现为Ca-P>Fe/Al-P>OP，表明该研究区域沉积物以Ca-P占优势。金山湖表层沉积物pH值呈现弱碱性，通过Ca-P直接释放到上覆水中的磷较少，故金山湖沉积物磷元素的潜在风险较小。各形态磷的相关性分析结果发现，冬季沉积物TP与Fe/Al-P、IP呈极显著正相关（P<0.01）。夏季沉积物TP与IP、Fe/Al-P之间呈极显著正相关（P<0.01），与Ca-P呈显著正相关（P<0.05）。此外，金山湖沉积物OP、Fe/Al-P以及Ca-P的来源不一致。pH值对沉积物IP会产生一定影响，而其余磷形态则受pH值的影响程度较小。     

徐州九里湖沉水植物对富营养化湖泊的生态改善作用

为探究沉水植物对富营养化湖泊的生态改善作用，于2021年9月—2022年8月对徐州九里湖有、无沉水植物区的水质、沉积物磷形态、浮游植物群落分别进行监测。结果表明，九里湖沉水植物能够增加水体的透明度（SD）和溶解氧（DO），对总氮（TN）有一定程度的削减作用，对总磷（TP）、氨氮（NH₃-N）和浊度（TUB）的改善效果最明显，能够有效降低九里湖的富营养化水平。九里湖沉积物中无机磷（IP）对TP含量的贡献最大，占比为64.2%～93.2%。IP当中的盐酸提取磷（HCl-P）占绝对优势。有沉水植物区沉积物中TP和有机磷（OP）含量整体略高于无沉水植物区，说明沉水植物对上覆水中的磷元素沉降有一定的促进作用。九里湖全年共监测到浮游植物7门63属93种，群落密度为2.94×10⁶～7.0×10⁷个/L。除水温较低的1—4月外，蓝藻门中的假鱼腥藻（Pseudanahaena sp.）是其中的优势种。低温情况下，浮游植物密度整体大幅降低，但是绿藻门和硅藻门占比明显提升。沉水植物对浮游植物生长具有很好的抑制作用。香农-维纳（Shannon Wiener）多样性指数结果表明，沉水植物对浮游植物多样性有降低作用。     

洪泽湖沉积物中磷的形态研究

采用改进的七步连续提取法对洪泽湖9个采样点沉积物中的各形态磷进行了分析,结果表明,所测洪泽湖沉积物中总磷(TP)含量范围为580.7～1 447.7 mg/kg,无机磷(IP)是TP的主要部分,占TP含量的64.32％～88.60％;有机磷(0P)占TP的11.40％～35.68％.受河流注入和人为活动的影响,TP、I...     

溪源水库蓄水前后冬春季水体营养盐和浮游植物特征研究

于2007—2008年溪源水库蓄水前,2014—2015年溪源水库蓄水后对溪源宫水源地水体进行采样,分析了冬春季水体的理化指标、浮游植物生物量及群落组成。蓄水前共鉴定出浮游植物6门26属43种,水体水质状况较好,浮游植物细胞密度平均为7.31×10~5cells/L,以硅藻、绿藻门为优势门类,两者占浮游植物总生物量的比例约为54.7%、32.2%,水体呈贫-中营养状态。蓄水后,水体氮、磷营养盐浓度分别约为蓄水前的2.4倍、3倍,浮游植物细胞密度平均为1.42×10~7cells/L,约为蓄水前的20倍,且群落结构发生改变,优势门类为硅藻、蓝藻、绿藻,所占比例分别为40.2%、38.7%、14.4%,蓝藻门比例有显著提高,约为蓄水前的5倍。说明建库蓄水对浮游植物的影响显著。     

太湖氮磷大气干湿沉降时空特征

为了探索太湖氮磷营养盐干湿沉降特征及对太湖营养盐输入的贡献，于2011年不同季节采集太湖不同位点的大气干湿沉降样品，分析干湿沉降中氮（N）和磷（P）的形态和沉降量。研究结果表明，输入太湖的磷以干沉降为主，而氮以湿沉降为主。在太湖干沉降中总无机氮（TIN）占总氮（TN）的77.1%，溶解性磷（DIP）占总磷（TP）的77.9%。干沉降中TIN主要以NH+4-N为主。西太湖是TN与TP通过大气干湿沉降输入太湖的最高湖区。太湖全年大气TN沉降总量为20 978 t，TP沉降总量为1 268 t，因此，氮磷大气干湿沉降是太湖营养盐输入的重要来源之一。     

万峰湖水体浮游植物调查及富营养化评价

通过2016年枯水期和丰水期对万峰湖水库浮游植物及水质理化指标采样分析,并应用综合营养状态指数对其水质营养状态进行评价。结果表明,万峰湖枯水期主要以硅藻为主,丰水期以绿藻和甲藻占优势;水体水质处于中营养化状态。相关性分析表明,浮游植物丰度在枯水期与各理化指标相关性不显著,在丰水期与DO、TP呈正相关,与IMn、Chla呈显著正相关。典范对应分析(CCA)表明,TN、SD和pH值是影响该水域浮游植物分布格局的重要因子,且CCA排序图较好显示了浮游植物分布和环境因子之间的关系。     

太湖水体溶解态磷的时空变化特征

对2010年太湖西岸区北段、湖心北区、贡湖、梅梁湾、竺山湾、西岸区南段、湖心南区、南岸区和湖心区9个研究点位水体中的溶解态总磷(TSP)、溶解态反应磷(SRP)和叶绿素a(Chl-a)进行了长达1年的动态监测,全面分析了太湖不同月份、不同区域水体溶解态磷含量的时空动态变化特征及其与藻类生长的相关性。全湖月平均TSP变化范围为(0.027±0.019)~(0.054±0.042)mg/L,SRP变化范围为(0.009 ± 0.006)~(0.035 ± 0.020) mg/L,夏秋季SRP含量高于春冬季。北太湖区溶解态磷含量普遍高于南太湖区,近岸溶解态磷含量高于离岸。各点位年均TSP变化范围为(0.019±0.011)~(0.104±0.038) mg/L,SRP变化范围为(0.009±0.006)~(0.041±0.022)mg/L。全年SRP变异(53.2%)高于TSP(23.4%)、近岸变异高于离岸、表层高于底层。溶解态磷含量日变化特征不明显,外源磷输入影响太湖水体溶解态磷分布。全年中太湖水体TSP、SRP与Chl-a呈显著正相关,相关系数分别为0.313(P<0.01)、0.284(P<0.01)。     

废水和地表水中磷的形态分析

废水和地表水中磷的形态分析陶大钧（江苏省无锡市环境科学研究所２１４０２３）龚娴芙，朱本兴（江苏省江阴市环境监测站２１４４３１）１前言在废水和地表水中，磷几乎部以各种磷酸盐的形式存在，有正磷酸盐，焦磷酸盐，偏磷酸盐，多磷酸盐和有机结合的磷酸盐，特殊情况...     

Eutrophication induced changes in benthic community structure of a flow-restricted tropical estuary (Cochin backwaters), India

The influence of anthropogenic loading on the distribution of soft bottom benthic organisms of a tropical estuary (Cochin backwaters) was examined. The industrial activities were found to be high in the northern and central part of the estuary, where dissolved inorganic nitrogen (DIN > 210 ??M) and phosphorus (DIP > 6.5 ??M) have caused high abundance of chlorophyll a (up to 73 mg m^???3) and accumulation of organic carbon in sediments (up to 5%). Principal component analysis distinguished three zones in the estuary. The central zone (Z1) was characterized by organic enrichment, low species diversity, and increased number of pollution tolerant species. Long-term deterioration of the estuary is indicated by an increase in the nutrients and chlorophyll a levels by sixfold during the last few decades. Flow restrictions in the lower estuary have lead to a fourfold increase in sediment organic carbon over the period of three decades. The reduced benthic diversity followed by an invasion of opportunistic polychaetes (Capitella capitata), are indicative of a stress in the estuary.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

Assessment of dissolved heavy metal in the Yangtze River estuary and its adjacent sea, China

The purpose of this paper is to determine the concentrations of dissolved heavy metals namely mercury (Hg), lead (Pb), cadmium (Cd), and copper (Cu) and to investigate the relationships between nutrients (nitrate-nitrogen and phosphate) and dissolved heavy metals. For this purpose, the concentrations of dissolved heavy metals were measured through 51 voyages form 1984 to 2006 in the Yangtze river estuary and its adjacent sea. Results analysis showed that dissolved heavy metals were not the main pollutants in the Yangtze river estuary, and the main source of heavy metal contamination was industrial wastewater from terrestrial pollution during the past 20 years. Heavy metal values showed significant abundance in the south branch of the Yangtze River estuary and Hangzhou Bay. In addition, Pb showed negative correlation with nutrients, while the positive correlations between Hg, Cd, and nutrients were shown. The obtained molar ratios, $\Delta \mbox{Cd}/\Delta \mbox{N} = 1.68 \times 10^{-5}$ and $\Delta \mbox{Cd}/\Delta \mbox{P} = 1.66 \times 10^{-4}$ , are close to those in plankton, showing the biogeochemical behavior and process of dissolved cadmium.     

洪湖水质空间特异性及主导因子分析

运用聚类分析和主成分分析方法对洪湖湿地12个采样点的理化特性进行分析。聚类分析表明,根据各采样点水质组分的相似性将洪湖大致分为3个空间区域,各空间区域正好分属于核心区、实验区、河口区,各区域间特征差异显著。对各区域水质的主成分分析表明,洪湖不同空间区域水质信息差异很大。第1组核心区主要体现富营养化信息;第2组实验区主要体现总氮、氧化还原电位、浊度信息;第3组河口区主要体现溶解氧及亚硝酸盐氮等污染物信息。揭示了洪湖水质现状及其成因,为洪湖水资源合理利用及生态保护提供基础数据。同时,运用地统计学方法为生态环境研究提供新的思路与方法。     

Dissolved oxygen content as an index of water quality in San Vicente Bay,Chile (36 degrees 45'S)

The present report describes some effects of industrial and municipal effluents on the waters of San Vicente Bay. Analyses ofthe main substances contained in the fishing industry effluentsuggest rating criteria based on the oxygen saturation of thewater as an assessment of organic pollution. Six cruises were carried out throughout the Bay, from June to December 1996. Watersamples were analyzed for dissolved oxygen, oil and grease content, and sediment samples for organic matter content. Waterparameters (salinity, temperature) were used to characterize theBay's hydrography, and to calculate values for oxygen saturation. The measurements demonstrated a local broad range of oxygen deficit, with a maximum of 45% in the winter to 95% in the spring. In November more than 65% of the Bay's area showed oxygendeficits greater than 40%. Organic matter was unusually high insediments along the northern sector of the Bay. The results suggest that the oxygen depletion was a representative parameterfor establishing a relative scale of water quality in this Bay.     

Stormwater metal loading to a well-mixed/stratified estuary (Sydney Estuary, Australia) and management implications

Stormwater modelling indicated an average annual discharge from Sydney estuary catchment of 215,300 mL and loadings of 0.8, 0.5, 1.7, 3.2, 1.1, 3.6 and 17.7 tonnes for As, Cd, Cr, Cu, Ni, Pb and Zn, respectively. Priority for remediation should be given to creeks with high-metal loads in the upper and central estuary, as well as discharging to the western shores of Middle Harbour. Managerial strategies need to target dissolved and particulate metal phases to ensure effective remediation. The proportion of metals discharged under low- (<5 mm rainfall/day), medium- (>5 to <50 mm/day) and high-flow conditions (>50 mm/day) was approximately 10%, 60% and 30% of total loading, respectively. Under high-flow conditions the estuary becomes stratified and most metals are exported to the sea, whereas metals discharged during low-flow may be remediated by infiltration. Effective remediation will depend on the extent to which ‘first-flush’ metals associated with medium-flow conditions can be remediated.     

Chromium redox speciation in natural waters

Dissolved hexavalent chromium concentrations were determined in river, estuarine and coastal waters of the Humber catchment in north-east England. Samples were collected, filtered, extracted on site and after storage for up to eight days. Hexavalent chromium concentrations did not change by more than 0.05 microg l(-1) (not significant, p = 0.05) over this period. Total chromium concentrations in the catchment were less than 1.0 microg l(-1). This is low in relation to the proposed Environmental Quality Standard. Hexavalent chromium accounted for between 27% and 100% of the total dissolved concentration, with an average of approximately 50%. The proportion of Cr(III) and Cr(VI) in the rivers and estuary were of the same range as previously measured in 1993. The addition of Cr(III) and Cr(VI) to fresh and saline water samples illustrates the complexity of the factors controlling chromium speciation in natural waters. The presence of oxidisable organic matter and the stabilising role of complexing organic ligands are proposed as the main controlling influences of redox speciation in filtered samples.     

A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

Dissolved organic iodine in marine waters: role in the estuarine geochemistry of iodine

Non-volatile dissolved organic iodine (DOI) can be a major, or even the dominant, species of dissolved I in coastal, inshore and estuarine waters. It can be converted to IO3- in the presence of an oxidizing agent and to I- by reacting it with a reducing agent. Depending on the exact experimental conditions, the yields of these reactions may not be quantitative. In previous analytical schemes for the determination of IO3-, I- and DOI in marine waters, if oxidation or reduction steps are involved and the concentrations of one or more species are estimated by difference, the presence of DOI can lead to an overestimation of the concentrations of the inorganic species determined by difference and an underestimation of the concentration of DOI. In two cruises covering the James River to the southern Chesapeake Bay and from the southern Chesapeake Bay to the Atlantic, above a salinity (S) of 2, the contribution of DOI to total I increased with decreasing salinity and reached a maximum of 80%. DOI, I- and IO3- were successively the dominant form of dissolved I at 0.1 < S < 15 in the James River estuary, 15 < S < 30 in the Southern Chesapeake Bay and S > 30 in the Atlantic Ocean at the Bay mouth, respectively. Total I behaved conservatively (i.e., no evidence of consumption or production) during estuarine mixing during both cruises. In the southern Chesapeake Bay, total inorganic I was also approximately conservative. The primary process affecting the speciation of dissolved I was the conversion of IO3- to I-. In the James River estuary, there were indications of the conversion of both IO3- and I- to DOI. The concentrations of total I, IO3-, I- and DOI in James River water were 0.121, undetectable, 0.068 and 0.053 microM, respectively. These concentrations of total I and I- are significantly higher while that of IO3- is noticeably lower than those used presently for estimating global riverine input of these I species to the oceans. The riverine flux of DOI to the oceans is presently unknown.     

Dual character of Sundarban estuary as a source and sink of CO2 during summer: an investigation of spatial dynamics

A comprehensive attempt has been made to evaluate the diurnal and spatial pattern of CO₂ exchange between the atmosphere and water along the estuarine track of Indian Sundarbans during the two summer months, April and May, 2011. Rigorous field observations were carried out which included the hourly measurements of total alkalinity, pH, fugacity of CO₂ in ambient air and water surface, dissolved oxygen, and chlorophyll a. The estuarine water was found rich in total alkalinity and was oversaturated with CO₂ throughout the diurnal cycle in the two stations situated at the inner and middle estuary, respectively, whereas an entirely reverse situation was observed in the outer fringes. The fugacity of CO₂ in water ranged from 152 to 657 μatm during the study period. The percentage of over-saturation in inner and middle estuary varied from 103 to 168 and 103 to 176 %, respectively, whereas the degree of under-saturation in the outer estuary lied between 40 and 99 %. Chlorophyll a concentrations were found higher in the outer estuary (12.3?±?2.2 mg?m^?3) compared to the middle (6.4?±?0.6 mg?m^?3) and inner parts (1.6?±?0.2 mg?m^?3), followed by a similar decreasing pattern in nutrient availability from the outer to inner estuary. The sampling stations situated at the inner and middle estuary acted as a net source of 29.69 and 23.62 mg?CO₂?m^?2 day^?1, respectively, whereas the outer station behaved as a net sink of ?33.37 mg?CO₂ m^?2 day^?1. The study of primary production and community respiration further supports the heterotrophic nature of the estuary in the inner region while the outer periphery was marked by dominant autotrophic character. These contrasting results are in parity with the source characters of many inner estuaries and sinking characters of the outer estuaries situated at the distal continental shelf areas.