PCBs and OCPs in human milk and selected foods from Luqiao and Pingqiao in Zhejiang, China

This study was conducted to measure the levels of 23 PCB congeners and 6 organochlorine pesticides (OCPs) in human milk and three food types collected from Luqiao and Pingqiao in Zhejiang Province, China. An effort was also made to explore the potential health risk for the mothers and breast-fed infants living in these two localities. Luqiao was selected as the sampling site because it is the largest place for the disassembly of obsolete transformers and electrical waste in China. Pingqiao, located 100 kin NW of Luqiao, is not known to be a place for any electronic or electrical waste and hence was chosen as the control site. Both localities are important agricultural places in the province. The organochlorines were measured in the samples using the GC-PECD technique. Micro-EROD bioassay method was also used as a complement of the chemical analysis to estimate the TEQ levels of dioxin-like PCBs in human milk. The data showed that the human milk, rice, hen egg, and fish samples from Luqiao were more heavily contaminated with PCBs than those from Pingqiao, suggesting that the mothers and their breast-fed infants in Luqiao tended to receive greater exposure to PCBs than those living in Pingqiao. The OCP levels in the two localities were found comparable, suggesting that the major source of contamination with these pesticides was from their agricultural uses. Significant correlation (R-2 = 0.87, P < 0.001) of PCB TEQs was found between the bioassay and chemical analysis method, suggesting that micro-EROD is an effective method for comprehensive determination of TEQ levels in human milk. Comparison with literature data showed that the PCB levels in milk samples from Luqiao were significantly higher than those from localities in other Chinese provinces and comparable to those in developed or industrialized countries. (c) 2007 Published by Elsevier B.V.

Induction of oxidative stress and apoptosis by PFOS and PFOA in primary cultured hepatocytes of freshwater tilapia (Oreochromis niloticus)

Perfluorinated organic compounds (PFOCs) are emerging persistent organic pollutants (POPs) widely present in the environment, wildlife and human. We studied the cellular toxicology of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) on oxidative stress and induction of apoptosis in primary cultured hepatocytes of freshwater tilapia (Oreochromis niloticus). Cultured hepatocytes were exposed to PFOS or PFOA (0, 1, 5, 15 and 30 mg L-1) for 24 h, and a dose-dependent decrease in cell viability was determined using trypan blue exclusion method. Significant induction of reactive oxygen species (ROS) accompanied by increases in activities of superoxide dismutase (SOD), catalase (CAT) and glutathione reductase (GR) were found, while activities of glutathione peroxidase (GPx) and glutathione-S-transferase (GST) were decreased. Glutathione (GSH) content was reduced following treatment of PFOA and PFOS. A dose-dependent increase in the lipid peroxidation (LPO) level (measured as maleic dialdehyde, MDA) was observed only in the PFOA exposure groups, whereas LPO remained unchanged in the PFOS exposure groups. Furthermore, a significant activation of caspase-3, -8, -9 activities was evident in both PFOS and PFOA exposure groups. Typical DNA fragmentation (DNA laddering) was further characterized by agarose gel electrophoresis. The overall results demonstrated that PFOS and PFOA are able to produce oxidative stress and induce apoptosis with involvement of caspases in primary cultured tilapia hepatocytes. (c) 2007 Elsevier B.V. All rights reserved.

Effects of brominated flame retardants and brominated dioxins on steroidogenesis in H295R human adrenocortical carcinoma cell line

Brominated flame retardants (BFRs) and brominated dioxins are emerging persistent organic pollutants that are ubiquitous in the environment and can be accumulated by wildlife and humans. These chemicals can disturb endocrine function. Recent studies have demonstrated that one of the mechanisms of endocrine disruption by chemicals is modulation of steroidogenic gene expression or enzyme activities. In this study, an in vitro assay based on the H295R human adrenocortical carcinoma cell line, which possesses most key genes or enzymes involved in steroidogenesis, was used to examine the effects of five bromophenols, two polybrominated biphenyls (PBBs 77 and 169), 2,3,7,8-tetrabromodibenzo-p-dioxin, and 2,3,7,8-tetrabromodibenzofuran on the expression of 10 key steroidogenic genes. The H295R cells were exposed to various BFR concentrations for 48 h, and the expression of specific genescytochrome P450 (CYP11A, CYP11B2, CYP17, CYP19, and CYP21), 3 beta-hydroxysteroid dehydrogenase (3PHSD2), 17 beta-hydroxysteroid dehydrogenase (17 beta HSD1 and 17 beta HSD4), steroidogenic acute regulatory protein (StAR), and 3-hydroxy-3-methylglutaryl coenzyme A reductase (HMGR)-was quantitatively measured using real-time polymerase chain reaction. Cell viability was not affected at the doses tested. Most of the genes were either up- or down-regulated, to some extent, by BFR exposure. Among the genes tested, 3PHSD2 was the most markedly up-regulated, with a range of magnitude from 1.6- to 20-fold. The results demonstrate that bromophenol, bromobiphenyls, and bromodibenzo-p-dioxin/furan are able to modulate steroidogenic gene expression, which may lead to endocrine disruption.

Effects of nonylphenol on the growth and microcystin production of Microcystis strains

Both organic pollution and eutrophication are prominent environmental issues concerning water pollution in the world. It is important to reveal the effects of organic pollutants on algal growth and toxin production for assessing ecological risk of organic pollution. Since nonylphenol (NP) is a kind of persistent organic pollutant with endocrine disruptive effect which exists ubiquitously in environments, NP was selected as test compound in our study to study the relationship between NP stress and Microcystis growth and microcystin production. Our study showed that responses of toxic and nontoxic Microcystis aeruginosa to NP stress were obviously different. The growth inhibition test with NP on M. aeruginosa yielded effect concentrations EbC50 values within this range of 0.67-2.96 mg/L. The nontoxic M. aeruginosa strains were more resistant to NP than toxic strains at concentration above 1 mg/L. Cell growth was enhanced by 0.02-0.2 mg/L NP for both toxic and nontoxic strains, suggesting a hormesis effect of NP on M. aeruginosa. Both toxic and nontoxic strains tended to be smaller with increasing NP. But with the increased duration of the experiment, both the cell size and the growth rate began to resume, suggesting a quick adaptation of M. aeruginosa to adverse stress. NP of 0.05-0.5 mg/L significantly promoted microcystin production of toxic strain PCC7820, suggesting that NP might affect microcystin production of some toxic M. aeruginosa in the field. Our study showed that microcystin excretion was species specific that up to 75% of microcystins in PCC7820 were released into solution, whereas > 99% of microcystins in 562 remained in algal cells after 12 days' incubation. NP also significantly influenced microcystin release into cultural media. The fact that NP enhanced growth and toxin production of M. aeruginosa at low concentrations of 0.02-0.5 mg/L that might be possibly found in natural freshwaters implies that low concentration of NP may favor survival of M. aeruginosa in the field and may play a subtle role in affecting cyanobacterial blooms and microcystin production in natural waters. (c) 2006 Elsevier Inc. All rights reserved.

Monitoring organochlorine pesticides and polychlorinated biphenyls in Baiyangdian Lake using microbial communities

We used polyurethane foam units (PFUs) to collect persistent organic pollutants (POPs) from four sites in Baiyangdian Lake in July 2003. Following extraction from the PFUs, relative concentrations of seven organochlorine pesticides (OCPs) and ten polychlorinated biphenyls (PCBs) were determined by gas chromatography. OCPs and PCBs were detected in the microbial communities from all the four sampling stations. In terms of the total concentration of POPs (OCPs+ PCBs), two river estuary stations had more POP (18.45 mu g/L and 9.77 mu g/L) than the two mid-lake stations (4.75 mu g/L and 5.21 mu g/L), indicating that Baiyangdian Lake was significantly impacted by inflow from the Fu River and Baigou River.

Hydroxylated metabolites of polychlorinated biphenyls and their endocrine disrupting mechanism

Hydroxylated polychlorinated biphenyls (OH-PCBs a group of main active metabolites of polychlorinated biphenyl (PCBs) which are typical persistent organic pollutants (Pops) I have been identified in wild animals and human. The endocrine disruption of OH-PCBs has been drawn great attention due to the similarity of their chemical structures to the natural estrogens and thyroid hormones. The metabolic pathways of PCBs, the levels of OHPCBs in organism, the endocrine disruption and other adverse effects of OH-PCBs are reviewed. The further investigation of OH-PCBs will not only reveal the toxicological mechanism of PCBs, but also can lay scientific basis for setting up the risk assessment of POPs contamination and early-warning system in China.

SESTON IN A SEASONALLY FLOODED LAKE OF THE CENTRAL CHANGJIANG RIVER (CHINA)

Seston was studied during inundation in a seasonally flooded lake of Changjiang River system (Lake Chenhu, Hanyang, P.R. China). Particulate organic matter (POM), particulate inorganic matter (PIM), particulate organic carbon (POC) and particulate organic nitrogen (PON) concentrations were highest upon initial inflow of river water, as a result of the riverine transport of allochthonous seston into the lake, and during the initial draining phase, coinciding with the postflood development of phytoplankton biomass and accumulation of detritus from the decomposition of the inundated vegetation grown during the preceding period of exposure. However seston concentrations were lowest shortly after the termination of flood inflow, presumably due to sedimentation and river water dilution. Seston food quality, based on POM : PIM, C : N and Algal-AFDW : POM ratios, was higher during the early high water phase than during the filling and draining phases.

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO2 sol-gels with various Ag/TiO2 molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO2 thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO2 nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO2 sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO2 sol-gel, four types of the TiO2 thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO,), TA (bottom layer was pure TiO,, surface layer was Ag modified), TT (pure TiO, thin film) and AA (TiO, thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I-ph). LSV confirmed the existence of Ago state in the TiO, thin film. SEM and XRD experiments indicated that the sizes of the TiO,, nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO2 thin film.

长期施肥对黑土POM分布及其碳水化合物特性的影响

本文以吉林省公主岭“国家黑土肥力与肥料效益长期定位监测基地”的黑土为材料，研究长期施肥对黑土POM的分布及POM（FPOM和OPOM）中碳水化合物特性的影响，结果表明： 有机肥及有机肥与化肥配施显著提高了土壤中碳水化合物的含量，促进了植物来源的中性糖和真菌来源的氨基糖在土壤中的积累。在有机质含量较高的黑土上长期施用高量有机肥会出现养分过剩的现象。不同施肥处理下黑土有机质中中性糖的相对含量与不施肥相比无显著变化，氨基糖的相对含量则显著增加。随着有机肥施用量的增加，土壤中中性糖的含量也随之显著增加，而氨基糖则没有明显变化。 有机肥及有机肥与化肥配施能显著增加黑土中POM以及POM-C、POM-N和碳水化合物的含量，且均随有机肥施用量的增加而增加。各个处理中OPOM的碳、氮和碳水化合物含量远远高于FPOM。POM中各个单糖对施肥的响应与碳水化合物的总量基本一致。单施高量有机肥及有机肥与化肥配施均能显著提高POM中中性糖和氨基糖占有机质的比例，单施低量有机肥对POM中氨基糖和FPOM中中性糖占有机质的比例作用不明显，而能显著增加OPOM中中性糖占SOM的比例。在POM的中性糖中葡萄糖和木糖对SOM的贡献较大，氨基糖中氨基葡萄糖的贡献较大。OPOM中碳水化合物对SOM的贡献大于FPOM。FPOM中中性糖主要来源于植物，而OPOM中则主要来源于植物和微生物。在短期范围内，施肥并没有引起POM中两种来源氨基糖比例的显著变化，而从长期来看，有机肥处理却使POM中细菌源氨基糖的积累得到了加强。单施化肥对黑土有机质和黑土POM的含量以及二者中的碳、氮和碳水化合物的含量和组成均没有显著的影响。

Determination of photochemically produced hydroxyl radicals in seawater and freshwater

A variety of short-lived, reactive chemical species (i.e. free radicals and excited state species) are known to be photochemically produced in natural waters. Some of these transients may strongly affect chemical and biological processes, and they have been implicated in the degradation of organic pollutants and natural organic compounds in aqueous environments. Previous studies demonstrated that the highly reactive hydroxyl radical (OH) is photochemically formed in seawater. However, the quantitative importance of this key species in the sea has not been previously studied because of past analytical limitations. By using a highly sensitive probe based on α-H atom abstraction from methanol, we were able to measure production rates and steady-state concentrations of photochemically produced OH radicals in coastal and open ocean seawater and freshwaters. The validity of the method was tested by intercalibrating with an independent, OH-specific reaction, hydroxylation of benzoic acid, and also by competition kinetics experiments. Our OH production rates and steady-state concentrations for freshwaters are in excellent agreement with those measured by previous investigators for similar waters. In contrast, for seawater, the values we measured are 1–3 orders of magnitude higher than previously predicted by models, indicating that there is a major unknown photochemical OH source (s) in seawater.

Benthic foraminiferal distribution in surface sediments along continental slope of the southern Okinawa Trough: dependance on water masses and food supply

Benthic foraminiferal analysis of 29 samples in surface sediments from the southern Okinawa Trough is carried out. The results indicate that benthic foraminiferal abundance decreases rapidly with increasing water depth. Percentage frequencies of agglutinated foraminifera further confirm the modem shallow carbonate lysocline in the southern Okinawa Trough. From continental shelf edge to the bottom of Okinawa Trough, benthic foraminiferal fauna in the surface sediments can be divided into 5 assemblages: (1) Continental shelf break assemblage, dominated by Cibicides pseudoungerianus, corresponds to subsurface water mass of the Kuroshio Current; (2) upper continental slope assemblage, dominated by Cassidulina carinata, Globocassidulina subglobosa, corresponds to intermediate water mass of the Kuroshio Current; (3) intermediate continental slope assemblage, dominated by Uvigerina hispida, corresponds to the Okinawa Trough deep water mass above the carbonate lysocline; (4), lower continental slope - trough bottom assemblage, dominated by Pullenia bulloides, Epistominella exigua and Cibicidoides hyalinus, corresponds to deep water mass of the Okinawa Trough; and (5) trough bottom agglutinated assemblage, dominated by Rhabdammina spp., Bathysiphon flavidus, corresponds to I strongly dissolved environment of the trough bottom. The benthic foraminiferal fauna in the southern Okinawa Trough are controlled jointly by water masses and food supply. Water temperature, oxygen concentration and carbonate dissolution of the water masses are important controlling factors especially for the continental shelf break and trough bottom assemblages. The food supply also plays an important role in these benthic foraminiferal assemblages along the western slope. of the Okinawa Trough. Both the abundance and the 5 assemblages of benthic foraminifera correspond well to the organic matter supply along the continental slope and a lateral transport of TSM (total suspended matter) and POC (particulate organic carbon) from the shelf break to the deep water is also an important food supply for benthic fauna in this region.

东海颗粒有机碳的研究

本文在整个东海范围内对颗粒有机碳、颗粒有机氮、ATP进行了测定，并通过ATP对颗粒有机碳中的生命与非生命部分进行了定量区分。春季表层颗粒有机碳的分布以东海陆架区中部为中心向周围递减，与ATP的分布特点相似，说明主要受生物活动影响，秋季表层颗粒有机碳的最高值出现在长江口，并且从江口向外海递减，这种分布特点主要是由长江径流和颗粒物的再悬浮造成的。发现春季颗粒有机碳与ATP在外陆架区的真光层中存在着良好的线性相关关系，秋季则未发现两者间的任何相关关系。但是，无论春秋，ATP与叶绿素a在真光层中均存在较好的线性相关关系，真光层以下各层则未发现这种关系。

东海颗粒有机碳通量的模式计算

本研究论文属于国家科学基金重点研究项目“东海关键海洋通量过程的研究”计划的一个组成部分，通过1998年夏季东海航次，测定了颗粒有机碳的(Particulate Organic Carbon)含量，并研究了东海夏季POC含量的分布特点以及影响因素。同时，通过模式计算了部分站位的POC的垂直表观通量。然后，根据海水悬浮物质、底质物和浮游生物中的DOC的含量，定量的研究了东海的再悬浮现象，计算得到32°N断面和PN断面部分站位的再悬浮比，并计算得到了这些站位的POC净垂直通量，使我们对东海的POC净沉积通量有了一个定量的认识和把握。通过研究，我们发现东海夏季的POC的分布特点是：（1）近岸区域有明显的高值区的存在，并随离岸距离的增加而降低，这主要是受长江径流的影响；（2）在以(32°N, 125°E-125.5°E)为中心的冷涡表层海域存在着另一个POC含量的高值区，随深度增加而降低，在25米层以下随深度的增加而增加，在近底层形成一个新的高值区，研究表明表层高值区主要受生物生长的控制，而底层的高值区的存在与该区域的涡动层或上升流的存在有一定的关系；（3）同时，在东海所研究的两个断面，TSM（Total Suspended Materials）和POC的含量之间表现出了较好的相关性。通过模式研究，计算了六个站位八个层次的POC的垂直通量，其垂直通量为12.43 mg·m~(-2)·d~(-1)-148.23 mg·m~(-2)·d~(-1)，最大值为148.23 mg·m~(-2)·d~(-1)，出现在107站(32°N, 125°E)10米层，最小值为12.43 mg·m~(-2)·d~(-1)，出现在111站(32°0.08N, 125°59.57'E)的底层。通过对东海再悬浮比率的定量研究，计算了五个站和个层次的再悬浮比率。结果表明：（1）表层海水中悬浮物质的再悬浮比率在47.4%-79.18%之间；底层的再悬浮比率在72.75%-96.96%之间；（2）再悬浮比率的最大值出现在106站(32°N, 124°30'E)的底层，而再悬浮比率的最小值出现在102站(32°N, 122°30'E)的表层。在POC重直通量和再悬浮模式计算的基础上，我们计算得到了六个站位八个层次的POC净垂直通量，颗粒有机碳的净垂直通量最大值出现在107站(32°N, 125°E)的10米层，为117.4 mg·m~(-2)·day~(-1)；最小值出现在111站(32°0.08'N, 125°59.57'E)的底层为0.79 mg·m~(-2)·day~(-1)。通过几个站位的模式计算估算了东海颗粒有机碳平均的净沉积通量，其大约为6.55 mgC·m~(-2)·day~(-1)，即2.39gC·m~(-2)·y~(-1)。从而使我们对东海的颗粒有机碳的净垂直通量有了一个定量的认识。

Effects of increased pCO(2) and temperature on the North Atlantic spring bloom. I. The phytoplankton community and biogeochemical response

The North Atlantic spring bloom is one of the largest annual biological events in the ocean, and is characterized by dominance transitions from siliceous (diatoms) to calcareous (coccolithophores) algal groups. To study the effects of future global change on these phytoplankton and the biogeochemical cycles they mediate, a shipboard continuous culture experiment (Ecostat) was conducted in June 2005 during this transition period. Four treatments were examined: (1) 12 degrees C and 390 ppm CO2 (ambient control), (2) 12 degrees C and 690 ppm CO2 (high pCO(2)) (3) 16 degrees C and 390 ppm CO2 (high temperature), and (4) 16 degrees C and 690 ppm CO2 ('greenhouse'). Nutrient availability in all treatments was designed to reproduce the low silicate conditions typical of this late stage of the bloom. Both elevated pCO(2) and temperature resulted in changes in phytoplankton community structure. Increased temperature promoted whole community photosynthesis and particulate organic carbon (POC) production rates per unit chlorophyll a. Despite much higher coccolithophore abundance in the greenhouse treatment, particulate inorganic carbon production (calcification) was significantly decreased by the combination of increased pCO(2) and temperature. Our experiments suggest that future trends during the bloom could include greatly reduced export of calcium carbonate relative to POC, thus providing a potential negative feedback to atmospheric CO2 concentration. Other trends with potential climate feedback effects include decreased community biogenic silica to POC ratios at higher temperature. These shipboard experiments suggest the need to examine whether future pCO2 and temperature increases on longer decadal timescales will similarly alter the biological and biogeochemical dynamics of the North Atlantic spring bloom.

Distribution of calcifying and silicifying phytoplankton in relation to environmental and biogeochemical parameters during the late stages of the 2005 North East Atlantic Spring Bloom

The late stage of the North East Atlantic (NEA) spring bloom was investigated during June 2005 along a transect section from 45 to 66 degrees N between 15 and 20 degrees W in order to characterize the contribution of siliceous and calcareous phytoplankton groups and describe their distribution in relation to environmental factors. We measured several biogeochemical parameters such as nutrients, surface trace metals, algal pigments, biogenic silica (BSi), particulate inorganic carbon (PIC) or calcium carbonate, particulate organic carbon, nitrogen and phosphorus (POC, PON and POP, respectively), as well as transparent exopolymer particles (TEP). Results were compared with other studies undertaken in this area since the JGOFS NABE program. Characteristics of the spring bloom generally agreed well with the accepted scenario for the development of the autotrophic community. The NEA seasonal diatom bloom was in the late stages when we sampled the area and diatoms were constrained to the northern part of our transect, over the Icelandic Basin (IB) and Icelandic Shelf (IS). Coccolithophores dominated the phytoplankton community, with a large distribution over the Rockall-Hatton Plateau (RHP) and IB. The Porcupine Abyssal Plain (PAP) region at the southern end of our transect was the region with the lowest biomass, as demonstrated by very low Chla concentrations and a community dominated by picophytoplankton. Early depletion of dissolved silicic acid (DSi) and increased stratification of the surface layer most likely triggered the end of the diatom bloom, leading to coccolithophore dominance. The chronic Si deficiency observed in the NEA could be linked to moderate Fe limitation, which increases the efficiency of the Si pump. TEP closely mirrored the distribution of both biogenic silica at depth and prymnesiophytes in the surface layer suggesting the sedimentation of the diatom bloom in the form of aggregates, but the relative contribution of diatoms and coccolithophores to carbon export in this area still needs to be resolved.