Phosphorus fractions and its release in the sediments of Haihe River, China

The amounts and forms of phosphorus (P) in surface sediments of Haihe River, Tianjin, North China, were examined using a sequential chemical extraction procedure. Five fractions of sedimentary P, including loosely sorbed P (NH4Cl-P), redox-sensitive P (BD-P), metal oxide bound P (NaOH-P), calcium bound P (HCl-P), and residual P (Res-P) (organic and refractory P), were separately quantified. The results indicated that the contents of di erent P fractions in the sediments varied greatly. The total P (TP) contents ranged from 968 to 2017 mg/kg. Phosphorus contents in NH4Cl-P, BD-P, NaOH-P, and HCl-P ranged from 6.7 to 26.6 mg/kg, 54.5 to 90.2 mg/kg, 185.2 to 382.5 mg/kg, and 252.3 to 425.5 mg/kg, respectively, which represented 1.2%–3.2%, 7.7%–13%, 33.3%–48.9%, and 36.2%–54.2% of the sedimentary inorganic P, respectively. For all the sediment samples, the rank order of P-fractions was Res-P > HCl-P > NaOH-P > BD-P > NH4Cl-P. The highly positive relationship between the amounts of P released from the sediments and those in the NH4Cl-P and BD-P fractions, indicated that NH4Cl-P and BD-P were the main fractions that can release P easily.     

海河干流及河口地区土壤中有机氯农药的分布特征

以海河干流沿岸及海河河口周边地区为研究区域,采集了31个表层土壤样品,利用加速溶剂萃取（ASE）技术,使用气相色谱-电子捕获检测器（GC-ECD）分析方法测定了样品中的六六六（HCHs）和滴滴涕（DDTs）的含量.结果显示,海河河口地区土壤中HCHs和DDTs的含量范围分别为n.d.～1 728 μg·kg^-1（平均含量为93.9 μg·kg^-1）和n.d.～288 μg·kg^-1（平均含量为34.4 μg·kg^-1）.其中HCHs占优势,约占有机氯农药（OCPs）总残留量的72%.从海河干流到河口地区,OCPs的含量分布呈非均一性,受污染点源的分布影响较大,农药化工企业分布的区域土壤中的有机氯农药含量明显高于其它区域,海河干流区域相对高于河口地区.土壤中有机氯农药的成分分析结果表明,该地区土壤中除个别采样点OCPs仍有新的污染源输入外,大部分点位土壤中的OCPs主要来自于工业点源的历史输入和农业面源即有机氯农药的历史施用.与国内外其他地区土壤相比,该地区土壤中OCPs污染处于较高水平.     

海河流域农村非点源污染现状及空间特征分析

采用污染排放系数法估算了2008年海河流域农村生活源、畜禽分散养殖、农田化肥流失3个主要农村非点源COD、TN、TP和NH3-N 4种污染物的排放量,并对其排放强度和空间分布特征进行了分析.结果表明,海河流域农村非点源污染源排放COD、TN、TP和NH3-N总量分别为2435826, 3042079, 540568, 1798760t/a,平均排放强度分别为11.10, 13.97, 2.98, 8.28t/(km2·a).海河流域内河北省的3个农村非点源的4种污染物排放量均居首位,农村居民生活源对海河流域非点源污染贡献最大,是流域非点源污染控制最主要的对象;子牙河水系农村非点源污染物排放总量最大,而徒骇马颊河水系排放强度最大,是海河流域内污染最严重的水系,其首要非点源污染源是山东省的农村生活源.流域内非点源污染排放量和排放强度均呈现区域性分布,山区和平原区分别呈现出低污染等级和高污染等级.     

Limitation of spatial distribution of ammonia-oxidizing microorganisms in the Haihe River, China, by heavy metals

The Haihe River is characterized by high ammonia pollution. Therefore, it is necessary to determine how environmental factors, such as heavy metals in the river limit the spatial distribution of ammonia-oxidizing microorganisms. In this study, the relationships between five heavy metals and ammonia-oxidizing microorganisms were studied. The results showed that under high ammonia, low oxygen and high concentrations of suspended particles, ammonia-oxidizing bacteria(AOB) ranged from 101:3 to 104:8 gene copies/mL and ammonia-oxidizing archaea(AOA) ranged from 102:7 to 104:9 gene copies/mL. The average metal concentrations in water were 23.57(Cr), 21.58(Ni), 65.09(Cu), 622.03(Zn) and 10.16(As) μg/L, with those of Zn, Cu and Cr being higher than the US EPA criteria. Scatter plots of microbial abundance and metals indicated that both AOA and AOB were limited by heavy metals, but in different ways. As had an inhibitory effect on AOB, while Ni and Zn promoted AOA, and the other metals investigated showed no significant correlation with microbial abundance. Overall, our results indicated that the effects of heavy metals on ammonia-oxidizing microorganisms in water are complex, and that the final effect is determined by the physiological role of each element in the microorganisms, as well as environmental conditions such as complexation of organic matter, not simply the total metal concentration.     

海河流域氮磷面源污染空间特征遥感解析

以MODIS遥感数据为驱动,采用以遥感像元为基本模拟单元的DPeRS（Diffuse pollution estimation with remote semsing）面源污染负荷估算模型,分析了2016年海河流域氮磷面源污染空间分布特征,并对“十三五”《重点流域水污染防治规划》中划定的海河流域172个控制单元进行面源污染优先控制单元分析.结果表明,2016年海河流域总氮（TN）排放量为13.62万t,入河量为2.53万t;总磷（TP）排放量为8152t,入河量为1597t;空间分布上,海河流域中部和南部地区氮磷面源污染较重,其中河北省片区氮磷面源污染物排放量及入河量最大;农田径流型是海河流域氮磷面源污染的主要类型,其次城镇径流影响也较大;筛选出海河流域TN和TP面源污染优先控制单元分别为127和131个,面积占比分别为84.2%和87.0%.     

海河流域河流富营养化程度总体评估

以海河流域2009年地表水水质现状数据为基础,分别运用河流水体富营养化潜势和浮游植物表征河流富营养化水平.结果显示,流域河流水体中富营养盐含量相对较高,河流水体中TN、NH3-N平均含量分别为8.13、4.34 mg·L-1,分别超过《地表水环境质量标准》(GB3838—2002)Ⅴ类限值(2 mg·L-1)4倍、2倍以上.北三河水系(北运河、潮白河、蓟运河)、子牙河水系和海河干流中TN浓度超过9 mg·L-1;海河流域河流水体中TP平均含量为0.87 mg·L-1,超过地表水Ⅴ类限值(0.4 mg·L-1)2倍以上.北三河水系、子牙河水系和黑龙港运东水系水中TP平均含量均超过1.0 mg·L-1.主要河流3%处于中或贫营养,44%处于极富营养化水平,主要分布在北三河水系、子牙河水系和漳卫河水系,表明流域河流总体呈现富营养化状态,平原段河流富营养化严重.河流治理要兼顾耗氧污染控制和营养盐控制,以改善河流水质.     

Persistent organochlorine residues in sediments of the Haihe River and Dagu Drainage River in Tianjin, China

Persistent organochlorine compounds were analyzed by means of GC-ECD in surface sediment samples from two selected rivers in Tianjin, Haihe River and Dagu Drainage River. A total of 16 surface sediment sites were selected along the both rivers. The frequency of detection of T-HCH and T-DDT in sediment samples both was up to 100%, which illustrated that the contamination of HCH and DDT was widespread in Haihe and Dagu Drainage Rivers. Results indicated that the concentrations of various pesticides in sediments from Haihe River were in the range of 3.30-75.96 ng/g dw for T-HCH and 1.57-211.57 ng/g dw for T-DDT. Compared with Haihe River, Dagu Drainage River was contaminated by HCHs and DDTs along the all locations and the values of T-HCH and T-DDT residues in sediments ranged from 2.30 to 124.61 ng/g dw and from 11.28 to 237.30 ng/g dw, respectively, The possible pollution sources were analyzed through monitoring results of organochlorine pesticides（OCPs） residues in sediments from the two rivers. The investigation also indicated that HCH was still used as pesticide in Tianjin partial area.     

Characterization and distribution of polycyclic aromatic hydrocarbon in sediments of Haihe River, Tianjin, China

In this study sediment samples were collected from 13 sites of Haihe River in Tianjin City, China, sixteen of priority polycyclic aromatic hydrocarbons （PAHs） listed in USEPA were analyzed by means of GC-MS. The total concentrations of PAH ranged from 774.81 to 255371.91 ng/g dw, and two to four rings of PAHs were dominant in sediment samples. Molecular ratios, such as phenanthrene/anthracene, fluoranthene/pyrene and low-molecular-weight PAH/high-molecular-weight PAH, were used to study the possible sources of pollution. It indicated a mixed pattern of parolytic and petrogenic inputs of PAHs in sediments in Haihe River. The petrogenic PAHs may be mainly derived from the leakage of refined products, e.g., gasoline, diesel fuel and fuel oil vehicle traffics or gas stations from urban area. The pyrolytic PAHs might be from the discharge of industrial wastewater and the emission of atmospheric particles from petrochemical factories. In addition, the levels of PAHs in the urban and industrial areas are far beyond the values reported from other rivers and marine systems reported. This situation may be due to polluted discharging from some petrochemical industrial manufactories and worse traffic conditions in Tianjin.     

海河流域不同植物砣含量、地域分异及其输入、输出量研究

海河流域是我国农业发展的一个重要基地,由于不合理开发利用,造成某些地区土壤出现贫瘠化、盐渍化和沙漠化,土壤缺磷也很明显.为了寻找植物对磷的需求特点以及海河流域土壤磷分布规律,可以从植物指示的角度研究不同地区不同植物磷含量特征及其差异,研究植物每年从土壤中输出和输入的磷总量,从而寻找农业生态系统磷循环规律并科学指导施肥.     

pH和盐度对海河干流表层沉积物吸附解吸磷(P)的影响

采用等温吸附解吸方法,研究大范围pH（2~12）和盐度（2‰~32‰）对海河表层沉积物吸附解吸磷的影响,并与分级提取技术得到的海河沉积物中磷形态分布相结合,进一步探讨磷在沉积物-水界面的迁移转化机理.结果表明,钙磷（Ca-P）和难溶态磷（Re-P）为海河表层沉积物磷的主要形态.沉积物对磷的吸附符合修正的Langmuir吸附等温线(R2>0.90).海河沉积物（8个典型断面）对磷的理论吸附量较大,说明在今后上覆水含磷浓度较高的情况下,沉积物仍能吸附大量的磷污染物.在海河水磷污染较轻的情况下,沉积物中的磷将释放并导致水体发生富营养化.pH对磷的吸附影响呈“U”型,且随着pH增大,磷的解吸量也增大,这是由于OH-交换能力的增强所致;盐度增大,沉积物对磷的吸附总体呈下降趋势,但在10‰~15‰之间有反复,并且随着盐度增大,磷的解吸量也下降.     

海河流域河流生态系统健康评价

随着经济发展,人类活动对河流生态系统的胁迫日益强烈,生态系统健康状况受到严重威胁.本研究以海河流域2010年73个采样点的水质、营养盐和底栖动物指标为例,采用指标体系法,从化学完整性和生物完整性两方面评价了流域内河流生态系统健康.结果表明,海河流域河流生态系统健康状况整体较差,有72.6%的样点处于"极差"健康状态,同时表现出明显的地区集聚效应;河流水质与人类活动强度密切相关;海河流域水体富营养化趋势明显;流域内底栖动物多样性低,清洁物种较少.氨氮、总氮、总磷等营养盐指标是影响河流生态系统健康的关键因子,应从控制上述指标入手,遏制海河流域河流生态系统健康恶化.对于河流生态系统健康评价,多因子的综合评价法优于单因子评价法.     

海河流域不同植物砣含量、地域分异及其输入、输出量研究

海河流域是我国农业发展的一个重要基地,由于不合理开发利用,造成某些地区土壤出现贫瘠化、盐渍化和沙漠化,土壤缺磷也很明显.为了寻找植物对磷的需求特点以及海河流域土壤磷分布规律,可以从植物指示的角度研究不同地区不同植物磷含量特征及其差异,研究植物每年从土壤中输出和输入的磷总量,从而寻找农业生态系统磷循环规律并科学指导施肥.     

海河及邻近海域表层沉积物重金属污染及其分布特征

对海河及邻近海域沉积物重金属污染程度进行调查,结果显示海河沉积物已遭受重金属污染,其重金属含量高于渤海湾,而且峰值最高的区域出现在工业发达、人口密集的天津市区和塘沽区。将海河及邻近海域表层沉积物不同颗粒组分的复合体进行分离,并进行了重金属含量的测定。结果进一步证明,重金属含量随沉积物复合体颗粒尺寸增大而减小。同时表明,渤海湾表层沉积物复合体比海河的颗粒大,砂质含量比海河高。渤海湾细小颗粒(<20μm)复合体含量(62.42%)低于海河(70.24%),而渤海湾粗砂(>200μm)组分(31.17%)比海河(17.83%)高得多。海河各粒级复合体上Cu、Pb、Cd的含量明显高于渤海湾中各粒级相应的重金属含量,平均是渤海湾的2倍左右,Cr在海河与渤海湾各粒级含量相对来说比较接近。     

海河流域植物中碳的输出(或存留)量和土壤中的库存量

研究了海河流域地区植物中碳的输出量和土壤库存量。结果指出：不同作物－土壤系统中各种作物碳的输出量和归还量有很大不同,作物碳输出量一般为归还量的３－１７倍;海河流域地区不同子流域土壤中碳的库存量也有差异,以滹沱河子流域土壤碳的库存量最高,大清河子流域土壤中碳的库存量最低。     

Spatial and vertical variations of perfluoroalkyl substances in sediments of the Haihe River, China

The levels of six perfluoroalkyl substances(PFASs) in surface sediment and their vertical variations in dated sediment cores from the Haihe River were investigated; studied substances included perfluorooctanoic acid(PFOA),perfluorononanoic acid(PFNA),perfluorooctane sulfonate(PFOS),perfluorodecanoic acid(PFDA),perfluoroundecanoic acid(PFUnA),and perfluorododecanoic acid(PFDoA). Results showed that the total PFAS concentration in surface sediment ranged between 0.52 and 16.33 ng/g dry weight(dw) with an average of3.47 ng/g dw,with PFOS and PFOA as the dominant PFASs. In general,the PFAS concentrations in the mainstream increased from the upper to the lower reaches,except that a drop occurred downstream of the Erdao dam. Although the PFASs in the sediment cores did not show a clear decreasing or increasing trend with depth,the three cores had a similar vertical variation.The PFAS levels were relatively low in the surface sediment,and reached the first high point at8–20 cm as a result of the wide use of PFASs from 1990 to 2000. After that the PFAS levels decreased,and then increased to a second high point at about 40–48 cm,which might be caused by the leaching of PFASs in sediment. Because PFASs have hydrophilic groups and relatively high solubility,the PFASs will transfer from the upper to lower layers of sediment when water infiltration occurs,leading to the fluctuation of PFAS levels in sediment cores. This study suggests that both the temporal variation of sources and transfer processes of PFASs in sediments are important factors influencing the vertical variation of PFASs in sediment cores.     

海河流域草地生态系统服务功能及其价值评估

草地生态系统为人类提供了畜产品和生命支持两个方面的多种服务功能,但人们常关注产品提供功能而忽视生命支持功能。研究采用联合国千年生态系统评估框架,构建了海河流域草地生态系统服务功能的评估指标体系,并以2005年为基准年,运用市场价值法、影子价格法等多种方法对海河流域草地生态系统进行经济价值评估。结果表明,海河流域草地面积为6.67×10¹⁰ m²,提供产品、固碳、保持土壤、净化环境等8项服务功能的总价值为2 216.28×10⁸元,单位面积价值为3.32元/(m²·a)。其中,提供产品的价值量最大,占总价值的31.3%,其次是固碳和营养物质保持功能的价值,分别占总价值的26.8%、22.2%。海河流域草地生态系统除了具有重要的产品提供功能外,固碳、营养物质保持等生命支持功能的巨大经济价值也不容忽视,平衡兼顾草地生态系统的产品提供功能和生命支持功能有助于促进海河流域经济社会发展与生态保护的协调。     

海河流域河流耗氧污染变化趋势及氧亏分布研究

耗氧污染是海河流域河流水污染的主要类型,耗氧污染物对河流溶氧的消耗产生的氧亏效应对水生生物产生重大影响.收集海河流域重点水功能区88个监测站点2000—2011年CODCr/CODMn、NH3-N指标,分析河流耗氧污染特征及演变趋势,并基于水质目标(2 mg·L-1)下计算出海河流域河流氧亏量.结果表明,流域河流耗氧污染总体呈现好转趋势,耗氧污染指标(NH3-N、CODCr/CODMn)逐渐降低,I~III类水质站点比例增加,劣V类水质站点数和超标倍数减少;CODMn降低幅度大于NH3-N,主要污染物由COD向NH3-N转化.海河流域重点氧亏区域主要集中于中部平原段和下游滨海段,未氧亏区域多集中于上游山区段;北三河、黑龙港运东与徒骇马颊河水系中部平原段整体处于缺氧区域,子牙河水系中部平原区缺氧现象最为严重,氧亏区域位于石家庄洨河下游、滏阳河艾辛庄下游至献县段及石津总干以南;海河流域内中部平原段河流氧亏的主要贡献仍以COD为主,但氨氮的贡献显著,其中黑龙港运东水系、徒骇马颊河水系和北三河水系,COD耗氧均值都高于5 mg·L-1,在北三河和子牙河水系,氨氮耗氧均值达到了4 mg·L-1.     

海河流域14条河流表层沉积物中多溴联苯醚的分布特征

海河流域是我国受人类活动扰动强度最大的地区,为了解多溴联苯醚（PBDEs）在该流域的污染现状与分布特征,通过采集14条主要河流的48个表层沉积物样品,采用高分辨的GC-MS/MS技术对干燥后的沉积物中27种PBDEs进行分析.结果发现沉积物中PBDEs的平均含量范围为0.06～2.10 ng·g^-1;其中徒骇河沉积物...     

海河流域典型河流粪源性指示微生物的污染特征及其时空分布

当前,我国河流污染的监测、研究与治理甚少考虑微生物指标,导致国内大多河流的微生物污染状况不明.本研究以海河流域上游山区段永定河(张家口市)、中游平原段温榆河(北京市)和下游滨海段北运河(天津市)3段典型河流为对象,选取粪大肠菌群、大肠杆菌、肠球菌、SC噬菌体为指示微生物指标,开展了历时1年的野外调查,以期明确海河流域典型河流微生物污染的浓度水平及其时空分布特征.结果表明:除有机污染和富营养化问题外,3条河流也受到了较为严重的微生物污染.监测断面的肠球菌、大肠杆菌、粪大肠菌群、SC噬菌体的年平均浓度分别在1.039×103~9.168×105CFU·L-1、10~1.870×106CFU·L-1、1.43×102~8.105×106CFU·L-1、0~4.77×106PFU·L-1之间.曼-惠特尼U检验分析结果表明,流域内指示微生物浓度分布的季节性变化不显著;3条河流中,中游平原段温榆河因受污水处理厂退水排入河道的影响,微生物污染水平最高;上游山区段永定河虽有机污染较轻,但动物粪便污染严重,导致河流微生物污染状况亦不容乐观.为保障流域公共卫生安全和地下水安全,上游山区段农村畜禽粪便处理、中游平原段污水处理厂退水应得到进一步的关注与管理.     

海河流域水生态功能一级二级分区

水生态功能分区是实现流域水环境"分区、分级、分期和分类"管理的基础.通过分析海河流域的陆地和水生态系统特点,确定了一级二级分区的指标体系,一级分区指标包括地貌类型、径流深、年降水量、年蒸发量,反映水资源供给功能的空间格局特征,共划分了6个一级水生态功能区;二级分区利用植被类型和土壤类型的空间异质性,反映流域生态水文过程及水质净化功能的空间格局特征,共划分了16个二级水生态功能区.最后,通过野外调查各个分区的水生态系统结构和生境差异性(水量、水质、河流生境、水生动植物等),对一级和二级分区结果进行了评价.分区结果能够为海河流域的水质目标管理和区域生态环境建设提供支持,分区方法和指标体系也可以为国内其它类似流域的水生态功能分区提供参考.