Assessing the quality of water quality assessments: An analytical quality control protocol for benthic diatoms

In this paper, the background to the development of an analytical quality control procedure for the Trophic Diatom Index (TDI) is explained, highlighting some of the statistical and taxonomic problems encountered, and going on to demonstrate how the system works in practice. Most diatom-based pollution indices, including the TDI, use changes in the relative proportions of different taxa to indicate changing environmental conditions. The techniques involved are therefore much simpler than those involved in many studies of phytoplankton, for example, where absolute numbers are required.

First Identification of the Hepatotoxic Microcystins in the Serum of a Chronically Exposed Human Population Together with Indication of Hepatocellular Damage

Hepatotoxic microcystins (MCs) are the most commonly reported cyanotoxins in eutrophic freshwaters. In 1996, human intoxications by MCs caused deaths of 76 patients at Caruaru dialysis centers in Brazil. So far, there have been no direct evidences of MC occurrence in human tissue in consequence of exposure to MC. In this study, we improved cleanup procedures for detecting MCs in serum sample using liquid chromatographymass spectrometry, and confirmed for the first time the presence of MCs in serum samples (average 0.39 ng/ml, which amounts to ca. 1/87 of the concentrations found in tissue samples of the Caruaru victims) of fishermen at Lake Chaohu. Daily intake by the fishermen was estimated to be in the range of 2.2-3.9 mu g MC-LReq, whereas the provisional World Health Organization tolerable daily intake (TDI) for daily lifetime exposure is 0.04 mu g/kg or 2-3 mu g per person. Moreover, statistical analysis showed closer positive relationships between MC serum concentrations and concentrations of alanine aminotransferase, aspartate aminotransferase, alkaline phosphatase, and lactate dehydrogenase than between the MC concentrations and other biochemical indicators. Thus, the data raise the question whether extended exposure in the range of the TDI or up to a factor of 10 above it may already lead to indication of liver damage. The results also demonstrate a risk of health effects from chronic exposure to MCs at least for populations with high levels of exposure, like these fishermen.

Distribution and bioaccumulation of microcystins in water columns: A systematic investigation into the environmental fate and the risks associated with microcystins in Meiliang Bay, Lake Taihu

For the purpose of understanding the environmental fate of microcystins (MCs) and the potential health risks caused by toxic cyanobacterial blooms in Lake Taihu, a systematic investigation was carried out from February 2005 to January 2006. The distribution of MCs in the water column, and toxin bioaccumulations in aquatic organisms were surveyed. The results suggested that Lake Taihu is heavily polluted during summer months by toxic cyanobacterial blooms (with a maximum biovolume of 6.7 x 10(8) cells/L) and MCs. The maximum concentration of cell-bound toxins was 1.81 mg/g (DW) and the dissolved MCs reached a maximum level of 6.69 mu g/L. Dissolved MCs were always found in the entire water column at all sampling sites throughout the year. Our results emphasized the need for tracking MCs not only in the entire water column but also at the interface between water and sediment. Seasonal changes of MC concentrations in four species of hydrophytes (Eichhornic crassipes, Potamogeton maackianus, Alternanthera philoxeroides and Myriophyllum spicatum) ranged from 129 to 1317, 147 to 1534, 169 to 3945 and 124 to 956 ng/g (DW), respectively. Toxin accumulations in four aquatic species (Carassius auratus auratu, Macrobrachium nipponensis, Bellamya aeruginosa and Cristaria plicata) were also analyzed. Maximum toxin concentrations in the edible organs and non-edible visceral organs ranged from 378 to 730 and 754 to 3629 ng/g (DW), respectively. Based on field studies in Lake Taihu, risk assessments were carried out, taking into account the WHO guidelines and the tolerable daily intake (TDI) for MCs. Our findings suggest that the third largest lake in China poses serious health threats when serving as a source of drinking water and for recreational use. In addition, it is likely to be unsafe to consume aquatic species harvested in Lake Taihu due to the high-concentrations of accumulated MCs. (C) 2007 Elsevier Ltd. All rights reserved.

In situ studies on the distribution patterns and dynamics of microcystins in a biomanipulation fish - bighead carp (Aristichthys nobilis)

The distribution and dynamics of microcystins in various organs of the phytoplanktivorous bighead carp were studied monthly in Lake Taihu, which is dominated by toxic cyanobacteria. There was a good agreement between LC-MS and HPLC-UV determinations. Average recoveries of spiked fish samples were 63% for MC-RR and 71% for MC-LR. The highest MC contents in intestine, liver, kidney and spleen were 85.67, 2.83, 1.70 and 1.57 mu g g(-1) DW, respectively. MCs were much higher in mid-gut walls (1.22 mu g g(-1) DW) than in hind- and fore-gut walls (0.31 and 0.18 mu g g(-1) DW, respectively), suggesting the importance of mid-gut wall as major site for MC absorption. A cysteine conjugate of MC-LR was detected frequently in kidney. Among the muscle samples analyzed, 25% were above the provisional tolerable daily intake level by WHO. Bighead is strongly resistant to microcystins and can be used as biomanipulation fish to counteract cyanotoxin contamination in eutrophic waters. (c) 2006 Elsevier Ltd. All rights reserved.

Effect of dietary cyanobacteria on growth and accumulation of microcystins in Nile tilapia (Oreochromis niloticus)

A 12-week growth trial was conducted in a flow-through system to investigate the chronic toxic effect of dietary intake of cyanobacteria on growth, feed utilization and microcystins accumulation in Nile tilapia (Oreochromis niloticus L.) (initial body weight: 5.6 g). Six isonitrogenous and isocaloric diets were formulated to include different contents of cyanobacteria with the dietary microcystins increasing from 0 to 5460.06 ng/g diet. The results showed that dietary intake of cyanobacteria could increase the growth of tilapia while there are no impacts on feed conversion efficiency or mortality. Feeding rate was higher for the diets containing highest cyanobacteria. Microcystins were mostly accumulated in fish liver. The relationship between microcystins contents in muscle, liver, spleen and dietary intake could be described by quadratic equations. Microcystins content in the muscle of Nile tilapia in present study exceeded the upper limit of the tolerable daily intake (TDI) of microcystins suggested by the WHO (0.04 mu g/kg body weight/d). It is suggested that Nile tilapia fed on toxic cyanobacteria is not suitable for human food. (c) 2006 Elsevier B.V. All rights reserved.

In situ studies on the bioaccumulation of microcystins in the phytoplanktivorous silver carp (Hypophthalmichthys molitrix) stocked in Lake Taihu with dense toxic Microcystis blooms

The phytoplanktivorous silver carp is an important biomanipulation fish to control cyanobacterial blooms and is also a food fish with the greatest production in China. The accumulation of the hepatotoxic microcystins (MCs) determined by LC-MS in various organs of silver carp was studied monthly in Lake Taihu dominated by toxic Microcystis aeruginosa. Average recoveries of spiked fish samples were 78% for MC-RR and 81% for MC-LR. The highest content of MCs was found in the intestine (97.48 mu g g(-1) DW), followed by liver (6.84 mu g g(-1) DW), kidney (4.8 8 mu g g(-1) DW) and blood (1.54 mu g g(-1) DW), and the annual mean MC content was in the order of intestine > liver > kidney > blood > muscle > spleen > gallbladder > gill. Silver carp could effectively ingest toxic Microcystis cells (up to 84.4% of total phytoplankton in gut contents), but showed fast growth (from 141 g to 1759 g in I year in mean weight). Silver carp accumulated less microcystins in liver than other animals in the same site or other fish from different water bodies at similar level of toxin ingestion. There was possible inhibition of the transportation of the most toxic MC-LR across the gutwall. Muscle of silver carp in Lake Taihu should not be consumed during period of dense Microcystis blooms while viscera were risky for consumption in more months. (c) 2006 Elsevier B.V. All rights reserved.

Using epilithic diatom communities to assess ecological condition of Xiangxi River system

Assessment method for ecological condition of Xiangxi River system was studied by using 13 candidate metrics of epilithic diatom which can reflect conditions in pH, salinity, nitrogen uptake metabolism, oxygen requirements, saprobity, trophic state, morphological character and pollution tolerant capability etc. By one-way ANOVA, the metrics of relative abundance of acidobiontic algae (ACID), freshwater algae (FRESH), high oxygen requirement (HIGH-O), eutraphentic state (EUTRA) and mobile taxa ( MOBILE) were suitable for distinguishing sites in different conditions. Then, the river diatom index (RDI) composed of these five metrics was used to evaluate ecological condition of the river. The results showed that the healthiest sites were in the Guanmenshan Natural Reserve ( with the mean RDI of 79.73). The sites located in tributary of Jiuchong River also owned excellent state (mean RDI of 78.25). Mean RDI of another tributary - Gufu River and the main river were 70.85 and 68.45 respectively, and the unhealthiest tributary was Gaolan River (with mean RDI of 65.64). The mean RDI for all the 51 sites was 71.40. The competence of RDI was discussed with comparison of evaluation results of DAIpo and TDI, it can be concluded that multimetrics is more competent in assessment task.

Seasonal dynamics of the hepatotoxic microcystins in various organs of four freshwater bivalves from the large eutrophic Lake Taihu of subtropical China and the risk to human consumption

So far, little is known on the distribution of hepatotoxic microcystin (MC) in various organs of bivalves, and there is no study on MC accumulation in bivalves from Chinese waters. Distribution pattern and seasonal dynamics of MC-LR, -YR and -RR in various organs (hepatopancreas, intestine, visceral mass, gill, foot, and rest) of four edible freshwater mussels (Anodonta woodiana, Hyriopsis cumingii, Cristaria plicata, and Lamprotula leai) were studied monthly during Oct. 2003-Sep. 2004 in Lake Taihu with toxic cyanobacterial blooms in the summer. Qualitative and quantitative determinations of MCs in the organs were done by LC-MS and HPLC. The major toxins were present in the hepatopancreas (45.5-55.4%), followed by visceral mass with substantial amount of gonad (27.6-35.5%), whereas gill and foot were the least (1.8-5.1%). The maximum MC contents in the hepatopancreas, intestine, visceral mass, gill, foot, and rest were 38.48, 20.65, 1.70, 0.64, 0.58, and 0.61 mu g/g DW, respectively. There were rather good positive correlation in MC contents between intestines and hepatopancreas of the four bivalves (r = 0.75-0.97, p < 0.05). There appeared to be positive correlations between the maximum MC content in the hepatopancreas and the delta(13)C (r = 0.919) or delta(15)N (r = 0.878) of the foot, indicating that the different MC content in the hepatopancreas might be due to different food ingestion. A glutathione (GSH) conjugate of MC-LR was also detected in the foot sample of C. plicata. Among the foot samples analyzed, 54% were above the provisional WHO tolerable daily intake (TDI) level, and the mean daily intakes from the four bivalves were 8-23.5 times the TDI value when the bivalves are eaten as a whole, suggesting the high risk of consuming bivalves in Lake Taihu. (C) 2005 Wiley Periodicals, Inc.

Tissue distributions and seasonal dynamics of the hepatotoxic microcystins-LR and -RR in two freshwater shrimps, Palaemon modestus and Macrobrachium nipponensis, from a large shallow, eutrophic lake of the subtropical China

So far no information is available on microcystin (MC) contents in shrimps, prawns or crayfish from natural freshwaters. Tissue distributions and seasonal dynamics of the hepatotoxic MC-LR and -RR in two freshwater shrimps, Palaemon modestus and Macrobrachium nipponensis were studied monthly (during June-November, 2003) in a Chinese lake containing toxic cyanobacterial blooms. The shrimps P. modestus and M. nipponensis accumulated high MCs not only in the hepatopancreas (mean 4.29 and 0.53 mu g g(-1) DW, respectively) but also in the gonad (mean 1.17 and 0.48 mu g g-1 DW, respectively), and the crayfish Procambarus clarkii accumulated as much as 0.93 mu g g(-1) DW in the gonad. This indicates that gonads of these invertebrates are the second important target organ of MCs. P. modestus apparently accumulated more MCs in their organs than M. nipponensis, which might be a reflection of their difference in trophic niche. Eggs of the shrimps accumulated 8.4% (M. nipponensis, 0.27 mu g g(-1) DW) and 29.0% (P. modestus, 2.34 mu g g(-1) DW) of total toxin burden, indicating that MCs had been transferred into offspring from their adults. Among the shrimp muscle samples analyzed, 31% were above the provisional WHO TDI level, suggesting the risk of consuming shrimps in Lake Chaohu. (c) 2005 Elsevier Ltd. All rights reserved.

Bioaccumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans in the foodweb of Ya-Er Lake area, China

Bioaccumulation of PCDD/F in the foodweb was investigated in the Ya-Er Lake area, which was heavily polluted by PCDD/F. The high concentrations of PCDD/F in sediment can be transferred and bioaccumulated by aquatic organisms and humans through various pathways. Benthonic invertebrate animals and aquatic plants with a lot of fibers in the root can accumulate PCDD/F from sediment and water. Snail (Bellamya aeruginosa), shrimp (Macrobranchium sp.) and freshwater mussel (Acuticosta chinensis (Lea)) took up PCDD/F from the water and maintained the emission patterns, whereas fish tended to selectively accumulate 2,3,7,8-substituted isomers. The tissues of fish-eating bird and duck (Anas platyrhynchos) were very highly contaminated by PCDD/F due to ingestion of fish and other aquatic organisms from sediment. The residual concentration in breast milk depended on the original concentration of PCDD/F in the food. A resident in Ya-Er Lake area showed a daily intake of PCDD/ F of about 9.14 pg TEQ/kg body weight/day. This is higher than the tolerable daily intake (TDI) for PCDD/F (1 pg TEQ/kg body weight/day), which was recommended by the World Health Organization (WHO). (C) 2001 Elsevier Science Ltd. All rights reserved.

I：端羟基液体聚丁二烯的氯化 II：氯化端羟基液体聚丁二烯的固化

合成了一系列氯含量不同的氯化丁羟（氯含量为5％～68％）。利用红外光谱、核磁共振观察了氯含量不同的氯化丁羟的双键变化。通过氯含量－5反应时间的关系及上述观察结果表明；丁羟在四氯化碳中进行氯化，首先进行加成反应，待双键饱和后，进行取代反应。用红外光谱观察了丁羟在氯化反应中三种微观结构的变化，观察了氯化高顺式聚丁二烯的双键变化，对氯化丁羟的赤苏异构体的碳－氯键红外光密度比值，进行了分析。这些观察和分析说明；丁羟在四氯化碳中氯化，存在着顺－反异构化反应。较详细地研究了影响交联反应的主要因素，利用低聚物的特点，通过数均分子量和粘度表征了交联反应程度。从而观察到，交联反应伴随着氯化反应之中，交联程度随着反应液中羟浓度的提高，随着反应时间的延长而增大。在一定反应液浓度下交联程度可以减小到很低程度，得到完全可溶的氯化丁羟。反应温度对交联反应在20～76℃范围无显著影响。提出了以氯乙醇为调节剂合成液体氯化丁羟的方法。实验结果说明，氯乙醇比文献中得到的乙醇在抑制交联反应，提高氯含量方面效果更好。氯化丁羟的羟值分析结果表明，丁羟的羟值在氯化反应中没有损失。这对氯化丁羟作为遥瓜型低聚物应用，在进行固化反应时，是非常重要的。随着溶剂介电常数的提高，出现凝胶的极限浓度也提高。根据这一实验和上述各项实验结果，基于烯类化合物氯化反应的一些基础研究工作。我们认为，在丁羟的氯化反应中，存在着两种反应机理；离子机理的加成，导致可溶氯化产物，自由基机理除加成外，导致交联，顺－反异构化反应。II 氯化丁羟与TDI的反应为二级反应。DBTDL（二月桂酸二丁基锡）对本固化反应有明显的催化效果。在100 ℃，以DBTDL为催化剂的固化反应中，氯化丁羟与TDI的反应速度常数为11.9 * 10~(-3)（升／克分子·秒），这个反应活化能为5.5千卡／克分子。合成了一系列的氯化丁羟聚氨酯。红外光谱测试结果表明，NH基分为两个红外吸收峰；3440 cm~(-1), 3310 cm~(-1)。高波频峰的为游离的NH基，低波频峰为缔合的NH基，其缔合度为88％。同时，表征了氯化丁羟聚氨酯的主要红外光谱吸收峰。研究了氯化丁羟聚氨酯的形态结构。透射电子微显镜示出氯化丁羟聚氨酯的微相分离区域结构，其硬段区域结构的尺寸大约趋于在0.7～1.6μ范围内（硬段含量30％）。差热分析和示差扫描量热分析结果一致表明，氯化丁羟聚氨酯在60 ℃-90 ℃范围内有一宽而弱的吸热转变区，在115 ℃左右有一吸热峰，它们归因于硬段区域结构的热转变。宽角X光衍射实验没有观察到明显的结晶吸收峰的存在。这个实验结果主要与氯化丁羟聚氨酯的无规、侧基及不对称的结构特点有关。初步实验结果显示出，氯化丁羟聚氨酯具有优异的粘结性能，其抗剪强度约是丁羟聚氨酯的六倍。通过氧化锌的作用，可以提高氯化丁羟聚氨酯的抗张强度。因为粘结强度是水轮机耐磨耐汽蚀涂层研制中比较关键的因素，所以，这个实验结果是很有意义的。

丁腈羟聚氨酯／聚甲基丙烯酸甲酯互穿网络高聚物的制备、形态和T_g转变行为的研究

采用同步法合成了丁腈羟聚氨酯[PU(HTBN)]/聚甲基丙烯酸甲酯(PMMA)互穿网络高聚物(IPN)，丁腈羟(HTBN)以甲苯二异氰酸酯(TDI)固化，PMMA的交联剂为二甲基丙烯酸-缩乙二醇酯(DEGDMA)。用H－500型电子显微镜(TEM)观察形态，用DDV－II型粘弹谱仪测定动态力学谱。实验结果表明，提高任一组分交联程度，均使体系的“强迫互容”性增加，PMMA相区可从3000～6000 A变成1000 A左右，加入与HTBN等当量的三羟甲基丙烷（TMP），或在DEGDMA用量为MMA重量的2％时，样品表现出两相连续性都较大的形态，两个T_g转变峰之间的Tanδ值也较高。提高腈其含量，可增加体系的化学相容性。当HTBN中丙烯腈含量约为24％时，表现为半相容体系。样品的Tanδ值在－20～＋120 ℃范围内，均在0.2～0.3上下，PMMA相区为200 A左右。在半相容体系中，“强迫互容”性对T_g较变行为和形态均有较明显影响。样品在动态力学谱上有两个转变峰，T_(g1)和T_(g2)，T_(g1)是PU（HTBN）的T_g转变，T_(g2)是PMMA的T_g转变。我们发现某些样品出现T_(g2)高于PMMA的T_g现象。通过对简化体系的研究表明，此现象与MMA跟HTBN上双键的反应有关，反应条件较激烈或1,2结构含量较高时，T_(g2)升高的幅度也较大。我们还制得一些阻尼特性较好的样品，它们具有用做吸振材料的可能性。

I 蓖麻油聚氨酯/聚甲基丙烯酸甲酯AB交联聚合物的研究 II 双阳原油热处理中加入降凝剂的研究

用蓖麻油与TDI反应生成端异氰酸酯基预聚物，再与HEA反应，生成端乙烯基预聚物，以不同比例的MMA与端乙烯基预聚物共聚交联，得到一组组成和交联密度各不相同的ABCP样品；为了分别观察组成和交联密度对材料性能的影响，在交联共聚过程中，以二乙烯基苯作交联点调节剂 ，得到固定组成，交联密度变化和固定交联密度组成变化的两组样品；此外，在固化过程中加入不同含量的丙烯酸（<10%），得到另一组样品，以观察氢键对该体系的影响。反应过程中用化学分析、NMR、IR及平衡溶胀等方法测定反应程度、分子量及交联网的交联密度；同时用动态粘弹谱仪和介电损耗仪测定样品的动态力学性能，转变与松弛及相容性；用材料试验机测试样品的力学性能；通过透射电子显微镜观察材料的形态结构。结果表明：copu/PMMA ABCP是个半相容体系，随硬段含量的增加和交联密度的减小相容性变差。形态结构呈不规则形状，相区尺寸由几A变至几百A，材料的力学性能和阻尼性能明显优子构成它们的均聚物。材料的阻尼值主要受交联密度的影响，玻璃化转变温度则主要受组成控制。氢键对该体系的形态结构有明显影响，丙烯酸含量为7.5%时相容性最差，5%和10%时最好。以双阳昌10号井原油为研究对象选用EVA作原料，以马来酸酐接枝改性，合成ET-6降凝剂。采取在热处理中加入降凝剂的综合处理方法，考察了降凝剂合成的最佳反应条件和降凝剂用量及热处理温度对原油结晶状态及流动性的影响。结果表明，热处理中加入ET-6降凝剂可使蜡的结晶形态发生明显变化，降凝剂用量仅100-500 ppm即可使双阳原油的凝固点由原来的30-31 ℃降至7-9 ℃，原油的低温流动性大为改观。

Microencapsulation of n-eicosane as energy storage material

For heat energy storage application, polyurea. microcapsules containing phase change material, n-eicosane, were synthesized by using interfacial polymerization method with toluene- 2,4-diisocyanate (TDI) and diethylenetriamine (DETA) as monomers in an emulsion system. Poly(ethylene glycol)octyl-phenyl ether (OP), a nonionic surfactant, was the emulsifier for the system. The experimental result indicates that TDI was reacted with DETA in a mass ratio of 3 to 1. FT-IR spectra confirm the formation of wall material, polyurea, from the two monomers, TDI and DETA. Encapsulation efficiency of n-eicosane is about 75%. Microcapsule of n-eicosane melts at a temperature close to that of n-eicosane, while its stored heat energy varies with core material n-eicosane when wall material fixed. Thermo-gravimetric analysis shows that core material n-eicosane, micro-n-eicosane and wall material polyurea can withstand temperatures up to 130, 170 and 250 degreesC, respectively.

Microencapsulation of n-hexadecane as a phase change material in polyurea

For thermal energy storage application, polyurea microcapsules about 2.5 mum in diameter containing phase change material were prepared using interfacial polycondensation method. In the system droplets in microns are first formed by emulsifying an organic phase consisting of a core material ( n-hexadecane) and an oil-soluble reactive monomer, toluene-2, 4-diisocyanate (TDI), in an aqueous phase. By adding water-soluble reactive monomer, diamine, monomers TDI and diamine react with each other at the interface of micelles to become a shell. Ethylenediamine (EDA), 1, 6-hexane diamine (HDA) and their mixture were employed as water-soluble reactive monomers. The effects of diamine type on chemical structure and thermal properties of the microcapsules were investigated by FT-IR and thermal analysis respectively. The infrared spectra indicate that polyurea microcapsules have been successfully synthesized; all the TG thermographs show microcapsules containing n-hexadecane can sustain high temperature about 300 degreesC without broken and the DSC measurements display that all samples possess a moderate heat of phase transition; thermal cyclic tests show that the encapsulated paraffin kept its energy storage capacity even after 50 cycles of operation. The results obtained from experiments show that the encapsulated n-hexadecane possesses a good potential as a thermal energy storage material.