Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (α-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (α-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for α-HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

Biofouling confounds the uptake of trace organic contaminants by semi-permeable membrane devices (SPMDs)

The outer layers of layflat, low density polyethylene plastic tubing (the principal component of semi-permeable membrane devices, SPMDs) were biofouled at a clean site in Hong Kong coastal waters for periods of 1–4 weeks. Following pre-fouling, triolein was added to the SPMDs and, along with control (unfouled) devices, they were exposed to a range of organochlorine pesticides (-HCH, aldrin, p,p^′-DDT) and PAHs (anthracene, fluoranthene and benzo(a)pyrene) under laboratory conditions. Results showed that the uptake of contaminants by SPMDs was severely reduced by as much as 50% under fouling conditions in comparison to unfouled controls. The ultimate utility of SPMDs as passive monitors is thus reduced, although alternative measures, such as the use of permeability reference compounds may compensate, and allow for realistic evaluations of dissolved environmental concentrations in aquatic environments. However, due to the complexities involved in such procedures––especially as they need to be conducted on a case-by-case basis––the utility of SPMDs appears to be limited for estimates of bioavailability unless necessary calibrations are undertaken within each environment that the sampler is used.     

Preliminary evaluation of the occurrence of herbicides and PAHs in the Wet Tropics region of the Great Barrier Reef, Australia, using passive samplers

The proximity of the Great Barrier Reef (GBR) Marine Park to areas of intensive agriculture and increasing urbanisation places the park under potential threat of contamination by land-based pollutants. Passive samplers were deployed at inshore reef and river mouth sites in the Wet Tropics region of the GBR during a dry and a wet season to measure levels of land-based organic pollutants in this environment. Two types of passive sampling devices were deployed: (i) a polar sampler, which can be used to monitor polar herbicides and (ii) semipermeable membrane devices (SPMDs) which sequester more hydrophobic compounds (e.g. PAHs, chlorpyrifos). Herbicides (diuron, simazine, atrazine, hexazinone and/or flumeturon) were detected at low concentrations (ng L⁻¹) at all sites sampled and in both seasons. Chlorpyrifos was not detected while PAHs were present in SPMDs at levels below limits of detection. The results show that the GBR environment does contain low levels of organic pollutants and that passive sampling provides a sensitive monitoring tool for measuring waterborne organic pollutants.     

A large excess of 210Po in the overlying water of the Zhubi Coral Reef flat, in the South China Sea

The temporal variability of ²¹⁰Po and ²¹⁰Pb was examined in the overlying water of the Zhubi Coral Reef flat to detect nutrient-like behavior of ²¹⁰Po. Different mechanisms influencing their geochemical behaviors were observed. Excess ²¹⁰Po relative to ²¹⁰Pb revealed an additional input of ²¹⁰Po other than in situ production from ²¹⁰Pb. The ²¹⁰Po input comes from the reef flat sediment through diffusion. The diffusion contributes 62% of the total ²¹⁰Po. This diffusion of ²¹⁰Po directly highlights its nutrient-like behavior. No input, but the slight removal, of ²¹⁰Pb was observed. Fractionation factors indicate that particulate matter prefers to adsorb ²¹⁰Po rather than ²¹⁰Pb. In combination with particulate composition, ²¹⁰Po diffusion was closely related to organic matter. These results reveal that ²¹⁰Po might be a potential tracer for quantifying nutrient recycling in the Coral Reef system.     

Measurement of O(1D) formation by ozone photolysis in the troposphere

An actinometric method to determine the rate constantk _1D of O(¹D) formation by ozone photolysis in the troposphere and at higher altitudes is presented. N₂O is used as a scavenger gas for O(¹D), and the molecular nitrogen product measured after gas chromatographic separation. First results of the method for ground level and for 26 km altitude are reported and compared with theoretical estimates ofk _1D for these levels.     

Strontium in rivers of the Baltic Basin

The rivers in the Baltic Basin drain a mixture of bedrocks ranging from Mesozoic-Paleozoic sediments in the south to Proterozoic-Archean intrusives in the north. The rivers in the sedimentary basin in the south have high concentrations of Sr, in the interval 100–500 µg l^–1 while the⁸⁷Sr/⁸⁶Sr ratio is close to that of seawater, i.e. 0.71. The northern rivers in the Precambrian shield area on the other hand have low Sr concentrations of 15–50 µg l^–1 with high⁸⁷Sr/⁸⁶Sr ratios of about to 0.73 (0.721–0.745). The riverine input of dissolved Sr to the brackish Baltic Sea approaches 60 tons year^–1, with a weighted mean concentration approaching 130 µg l^–1 and a weighted mean⁸⁷Sr/⁸⁶Sr ratio close to 0.712. Although the sedimentary area in the south supplies only about 43% of the total river discharge, it gives about 88% of the total Sr input. Because of this and the strong regional riverine variation in⁸⁷Sr/⁸⁶Sr ratio, Sr and its isotopes seem to be a convenient tool to unveil mixing relations of water masses in the northern Baltic Sea, provided high resolution analyses are applied. For an overall characterization of water mixing in the Baltic Sea, the Nd system will be superior to that of Sr.     

不同水体营养盐浓度下沉积物添加镧改性膨润土(Phoslock®)对轮叶黑藻(Hydrilla verticillata)生长的影响

轮叶黑藻(Hydrilla verticillata)是我国浅水湖泊常见的沉水植物,经常用于湖泊生态修复工程.然而在生态修复中后期,轮叶黑藻又往往会过度繁殖,影响其他湖泊功能的发挥.镧改性膨润土(锁磷剂)可以有效地降低沉积物中生物可利用磷含量,近年来被用于控制湖泊沉积物磷释放,其对轮叶黑藻生长和形态的影响还有待阐明.本研究在2种不同上覆水营养盐浓度条件下,设置添加和不添加锁磷剂2种处理,探究沉积物添加锁磷剂对轮叶黑藻生长及形态特征的影响.结果表明:1)沉积物添加锁磷剂之后,铁锰结合态磷、有机磷、铝结合态磷等生物可利用磷浓度显著降低,而生物不可用磷,如钙结合态磷浓度显著升高; 2)沉积物添加锁磷剂显著降低了轮叶黑藻的生物量和生长率.添加锁磷剂的处理组植物的株高、地上部分生物量均明显低于无锁磷剂组;相反,添加锁磷剂显著增加了植物的根长和地下部分生物量,进而提高了植物的根冠比; 3)锁磷剂对轮叶黑藻生长的影响程度与水体营养盐浓度有关,在低营养盐浓度水体中锁磷剂对植物生长和形态特征的影响更为显著.本研究表明,锁磷剂的添加能降低沉积物中生物可利用磷浓度,抑制轮叶黑藻的生长,同时这种影响程度与在水体营养盐浓度有关.     

利用210Pb、137Cs和241Am计年法测算云南抚仙湖现代沉积速率

通过对云南抚仙湖沉积物柱芯样品的210Pb、137Cs和241Am测试表明,柱芯剖面上有明显的1963年和1986年137Cs蓄积峰,验证了1975年次级蓄积峰存在的可能性,这些峰形完好的蓄积峰对抚仙湖的现代沉积环境有明显的时标意义。利用137Cs计年法得到抚仙湖沉积物自1963年、1975年及1986年以来到2007年的平均沉积速率分别为0.063g/(cm2·a)、0.052g/(cm2·a)和0.039g/(cm2·a),说明了过去近五十年抚仙湖沉积速率整体上经历了一个由快到慢的过程。借助于241Am 的1963年蓄积峰可以提高137Cs计年的准确性。根据210PbCRS计年模式,计算出每个样品深度所对应的年代,与137Cs计年法比较存在一定的偏差,分析了两种计年方法存在差异性的原因。通过质量深度和年代分析,抚仙湖的沉积速率变化幅度比较大,表明抚仙湖近129年来的沉积环境不稳定,可能与相应历史时期的人类活动有密切的关系。     

N2-Ar-He systematics and source of ore-forming fluid in Changkeng Au-Ag deposit, central Guangdong, China*

Changkeng Au-Ag deposit is a newly-discovered new type precious metal deposit. N₂-Ar-He systematics studies and³He/⁴He and δD- δ¹⁸O composition analyses show that the ore-forming fluid of the deposit is composed mainly of formation water (sedimentary brine) but not of meteoric water, which was thought to be source of the ore-forming fluid by most previous researchers. The content of mantle-derived magmatic water in the ore-forming fluid is quite low, usually lower than 10%. According to the source of the ore-forming fluid, the Changkeng Au-Ag deposit should belong to sedimentary brine transformed deposits. From the Late Jurassic to the Early Cretaceous Period, with deposition and accumulation of thick sediments in Sanzhou Basin, the formation water in the sedimentary layers was expelled from the basin because of overburden pressure and increasing temperature. The expelled fluid moved laterally along sedimentary layers to the margin of the basin, and finally moved upward along a gently-dipping interlayer fault. Because of a decline in pressure and temperature, ore minerals were deposited in the fault. Project supported by the National Natural Science Foundation of China (Grant No. 495020291, the Natural Science Foundation of Zhongshan University, the Research Foundation of National Key Laboratory of Metallogenesis in Nanjing University (Grant No. 039704) and the Lingnan Foundation.     

Variations of <Emphasis Type="Italic">δ</Emphasis><Superscript>18</Superscript>O in precipitation from the Muztagata Glacier,East Pamirs

Expeditions to Muztagata (in the eastern Pamirs) during the summer seasons of 2002 and 2003 collected precipitation samples and measured their oxygen isotopes. The δ ¹⁸O in precipitation displays a wide range, varying from −17.40‰ to +1.33‰ in June-September 2002 and from −22.31‰ to +4.59‰ in May-August 2003. The δ ¹⁸O in precipitation correlates with the initial temperature of precipitation during the observing periods. The positive correlation between δ ¹⁸O and temperature suggests that δ ¹⁸O can be used as an indicator of temperature in this region. The δ ¹⁸O values in fresh-snow samples collected from two snow events at different elevations on the Muztagata Glacier show a strong “altitude effect”, with a ratio of nearly −0.40% per 100 m from 5500 m to 7450 m.     

Hg2+对水鳖(Hydrocharis dubia)叶片生理生化及超微结构的毒害效应

研究了不同浓度Hg^2 对水鳖叶片光合放氧速率,呼吸速率、细胞膜透性、硝酸还原酶活性以及超微结构的毒害影响,结果表明,随着Hg^2 浓度的增加,水鳖叶片的光合放氧速率逐渐下降,呼吸速率、硝酸还原酶活性先升后降,而细胞膜透性则逐渐上升,电镜观察发现,水鳖叶细胞受Hg^2 毒初期,染色质凝集,叶绿体中类囊体片层以及线粒体嵴突膨胀,随着叶细胞遭受毒害程度的加深,核膜破裂,染色质与核质消失,叶绿体膨胀解体,线粒体空泡化。     

Potential toxicity of resuspended particulate matter and sediments: Environmental samples from the Bay of Banyuls-sur-Mer and Thermaikos Gulf

This contribution attempts to determine whether, and to what degree, environmental samples of resuspended particulate matter and sediments exert a toxicological impact. Further, an attempt is made also to screen the toxic level of potentially hazardous sites, based upon established sediment toxicity criteria. Therefore, a rapid, cost-effective and highly sensitive biotest (bioluminescence assay, based upon marine bacteria) has been applied on: biological fluid extracts; bottom sediments; and sediment trap samples. Samples were taken either from the Bay of Banyuls-sur-Mer (northwestern Mediterranean, France) or Thermaikos Gulf (northeastern Mediterranean, Greece). Biological fluid extracts and sediment trap samples corresponded to periods of resuspension events, or preceding and following such events.The results have revealed that the sampling strategy and biotest implemented in this study might be a useful tool for screening the toxicity of resuspended matter and sediments. Resuspension events appear to be able to exert an influence on the chemical forms of the micro-pollutants; thus on their bioavailability and toxicity. Nevertheless, based upon chemical analysis combined with the bioassay, the toxic level of the sediment samples could be determined, with the level at potentially hazardous sites being characterised.     

A survey to determine levels of chlorinated pesticides and PCBs in mussels and seawater from the Mid-Black Sea Coast of Turkey

A mussel and seawater monitoring survey was conducted at six sampling points between Yalikoy (Ordu) and Sinop in 1999-2000 along the Mid-Black Sea Coast of Turkey in order to assess concentrations of organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs). Chlorinated pesticides and PCBs were measured in the mussel Mytilus Galloprovincialis and in seawater. In the mussel samples, the most common pollutants in terms of average concentration per g of wet weight (ww), were DDT (max. 1800 pg/gww, min. 240 pg/gww) and its metabolites DDD (max. 5400 pg/gww, min. 240 pg/gww) and DDE (max. 2800 pg/gww, min. 70 pg/gww). Also, dieldrin, heptachlor and HCB were notable contaminants in the mussel samples. PCBs were determined in none of the biota or seawater samples. The concentrations of the OCs and PCBs in mussels were higher in coastal areas receiving river discharges and close to the largest city of the region, Samsun (especially in sampling points in the harbour area). The well-known long persistence of DDTs and other chlorinated compounds was confirmed by residues of these pollutants measured in mussels. On the other hand, even though the usage of such kind of persistent compounds in Turkey was banned, there may still be illegal usage and it is not certain whether the application of these compounds did end in the region.     

Distribution and bioaccumulation of polychlorinated biphenyls and organochlorine pesticides residues in sediments and Manila clams (Ruditapes philippinarum) from along the Mid-Western coast of Korea

The distribution and bioaccumulation features of PCBs, DDTs, and HCHs were investigated in the sediments and Manila clams collected from along the Mid-Western coast of Korea. The measured concentrations of ΣPCBs, ΣDDTs and ΣHCHs were 1.08–3.5, 0.12–0.35 and 0.090–0.30 ng g⁻¹ dw in sediment, and 33–390, 7.4–46 and 6.3–27 ng g⁻¹ lipid in Manila clam, respectively. Their levels were found to be relatively lower than those of other contaminated areas and the consumption of Manila clam from these areas seems to be safe for human health according to calculated lifetime cancer risk and hazard indices. The ΣPCBs and ΣDDTs concentrations in sediments showed a significant relationship to those in clams. The significant correlation was observed between BSAF in clams and K_ow for each PCB congeners and DDT metabolites. These findings support that the PCBs and DDTs levels, which are highly hydrophobic chemicals, in clam reflect the sediment pollution through bioaccumulation.     

底泥就地稳定化中零价铁(Fe0)对有机污染物的作用及其对上覆水体水质的影响

在实验室模拟静态湖泊体系条件下,通过向实际底泥中投加零价铁(Fe~0),考察反应前后底泥中有机物数量、种类、总有机质含量以及上覆水体溶解氧(DO)浓度、氧化还原电位(Eh)、pH和化学需氧量(CODCr)浓度等指标的变化,探讨Fe~0对底泥有机物的降解效果以及对上覆水体水质的影响.结果表明,投加Fe~0处理80 d后,(1)经GC-MS检测出底泥中易被降解的小分子有机物(分子量小于200)数量明显增多,底泥总有机去除率为44%.(2)上覆水体的DO浓度、Eh和pH都有不同程度的变化.DO浓度从6.6 mg/L迅速下降至0.2 mg/L,Eh从150 mV左右下降至74 mV,pH升高至8.4,此体系易形成厌氧环境;且上覆水体中CODCr低于纯底泥-水体系,上覆水中DO浓度、Eh及pH与CODCr浓度具有一定相关性.综上,底泥中投加Fe~0可有效降解有机物,且不会对上覆水体产生持久、较大的影响.     

Chlorinated compounds and polybrominated diphenyl ethers (PBDEs) in mussels (Mytilus galloprovincialis) collected from Apulia Region coasts

This project was carried out to assess the levels and spatial distribution of organochlorine compounds in the coastal marine environment, using mussels as bioindicators to evaluate the coastal water quality. Levels of polychlorobiphenils (PCB), chlorinated pesticides (DDT isomers, HCH isomers, Aldrin, Dieldrin, alfa-Endosulfan, Hexachlorobenzene, Pentachlorobenzene) and polybrominated diphenyl ethers (PBDEs) were determined in tissues from mussels (Mytilus galloprovincialis) collected along the Apulia Region coasts (Mediterranean Sea). Results indicate that contamination by organochlorine compounds is higher in mussels sampled in the Ionian Sea than in those from the Adriatic Sea, with PCB levels up to seven times higher in mussels from Ionian than from the Adriatic Sea. Although PCB levels were above the maximum values indicated by both European Community (EC) and National regulation in several sample sites, the PCB concentrations were particularly high in some stations, suggesting that these locations require a much specific attention. Conversely, results on the mussel contamination by PBDEs highlight their ubiquitous environmental distribution, and underline the need to establish the maximum level for these compounds in foodstuff, according to European Regulations.     

三峡水库枯水期补水调度对洞庭湖越冬白鹤(Grus leucogeranus)摄食栖息地的影响

摄食栖息地面积是反映越冬水鸟生存空间的直接指标,三峡水库运行后洞庭湖枯水期水文节律出现新的变化,给越冬水鸟摄食栖息地造成的影响尚不明确.为定量描述三峡水库枯水期不同出库流量对洞庭湖越冬水鸟摄食栖息地的影响,以洞庭湖典型的珍稀越冬水鸟——白鹤(Grus leucogeranus)为指示性候鸟,以白鹤摄食对栖息地水深需求作为关键生态因子,建立白鹤摄食对水深需求的栖息地适宜度模型.构建涵盖长江干流、三口河系、洞庭湖及其四水尾闾河段的江湖一体化耦合水动力模型,实现栖息地水动力分布特征的精确模拟.在此基础上耦合栖息地适宜度模型和水动力模型,建立了面向白鹤摄食对三峡水库出库流量需求的物理栖息地模型,量化不同出库流量对应的白鹤摄食栖息地加权可利用面积,定量分析水库运行对白鹤摄食栖息地面积的影响.结果表明:1月中旬三峡水库不同出库流量下洞庭湖白鹤潜在摄食栖息地面积保持稳定并随出库流量的增加呈增大趋势,维持在101.40~121.84 km²之间,其中东洞庭湖摄食栖息地面积在7.49~9.86 km²之间,南洞庭湖(含横岭湖)摄食栖息地面积在47.37~60.34 km²之间,西洞庭湖摄食栖息地面积在46.54~51.64 km²之间.不同湖区摄食栖息地面积随着三峡水库出库流量的增加均呈增大的趋势,说明三峡水库枯水期补水调度对于维持栖息地面积具有重要作用.较三峡水库运行前相比,白鹤摄食栖息地面积最大增加20.44 km²,对应的增幅为20.16%.成果明晰了三峡水库运行对洞庭湖白鹤摄食栖息地面积的影响规律,可为通过三峡水库补水调度改善洞庭湖越冬水鸟摄食栖息地生境提供理论基础.