长江口及其邻近海域沉积物磷的赋存形态和空间分布

采用SMT磷分级法研究长江口及其邻近海域沉积物中磷的赋存形态及分布特征,并探讨了其影响因子.研究结果表明,沉积物中总磷(TP)含量为476.91~980.04μg·g~(-1),有机磷(OP)含量为15.84~139.21μg·g~(-1);而无机磷(IP)为主要赋存形态,其含量为421.67~844.86μg·g~(-1),约占TP 72.9%~96.7%.IP中以钙结合态磷(HCl-P)为主,其含量为186.88~431.69μg·g~(-1),占IP的42.3%~57.79%;而铁/锰结合态磷(Na OH-P)的含量最少,其含量为4.17~52.76μg·g~(-1),仅占IP的2.0%~3.3%.空间分布上,不同形态磷含量具有明显的时空变化特征.夏季TP和IP的含量由咸水端到淡水端呈现出先降低后升高,冬季则先升高后降低的趋势.OP的含量在夏季时无明显分布规律,而在冬季时表现出由咸水端到淡水端降低的趋势.Na OH-P含量在冬夏季均表现为淡水端处较高;HCl-P含量在夏季无明显的变化规律,而冬季时近淡水端处较高.沉积物粒径大小影响磷的赋存形态,表现为夏季粘粒对OP影响较大;冬季粘粒和粉粒与IP存在着负相关性,与OP存在着显著的正相关性.此外,沉积物总有机碳、盐度和碱性磷酸酶活性也是影响磷赋存形态的主要因子.     

Organochlorine contaminants in different tissues from Platichthys flesus (Pisces,Pleuronectidea)

Polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) are organic contaminants that tend to accumulate in fish. Estuaries are exposed to high anthropogenic activities, therefore tending to accumulate more contaminants than the adjacent coastal waters. Platichthys flesus, a fish with high economic value, was analysed for PCBs and HCB along its different age groups, in liver, gills, gonads and muscle. Younger fishes were caught in the estuary, whereas older fishes were caught in the adjacent coastal waters and acquired at Figueira da Foz Regional Office of Docapesca-Portos e Lotas, SA. Both contaminants concentrations follow the pattern: liver > gills > muscle. Hepatosomatic index had the lowest values in younger fishes and the highest values in older fishes. Condition factor values remain stable with age. Younger fishes had higher PCBs concentrations than the older fishes. In opposition HCB was only detected in fish from 3+ to 5+ and its concentration tended to increase with age. Overall P. flesus is considered safe for human intake.     

Sediment-water distribution of perfluorooctane sulfonate (PFOS) in Yangtze River Estuary

Analysis of Perfluorooctane sulfonate (PFOS) distribution in water and sediment in Yangtze River Estuary showed that the estuary was a sink for PFOS. Salinity was an important parameter in controlling the sediment-water interactions and the fate or transport of PFOS in the aquatic environment. As the salinity (S‰) increased from 0.18 to 3.31, the distribution coefficient (K_d) between sediment and water linearly increased from 0.76 to 4.70 L g⁻¹. The study suggests that PFOS may be carried with the river water and transported for long distances before it reaches to the sea and largely scavenged to the sediment in the estuaries due to the dramatic change in salinity.     

Using sequential extraction techniques to assess the partitioning of plutonium and neptunium-237 from multiple sources in sediments from the Ob River (Siberia)

Sequential extraction techniques have been developed to assess partitioning of anthropogenic radionuclides (²⁴⁰Pu, ²³⁹Pu, and ²³⁷Np), originating from a variety of sources, as identified by using bulk sediment isotopic composition. Sediments were leached sequentially with a series of six chemical treatments designed to approximate different environmental processes that may occur or to selectively extract trace metals contained in different solid phases of the sediments (i.e., exchangeable, reducible, carbonate, organic, acid leachable, and refractory). Results indicate the majority of Pu and Np is similarly distributed within many of the extracted fractions, with the largest percentage (66–97%) of both elements being observed in sediments treated with buffered citrate dithionite (CDB), which targets easily reduced constituents such as Mn and Fe hydrous oxides. While these results do indicate an association of Pu and Np with redox sensitive elements, the environmental implications are unclear given that the CDB treatment is more extreme than naturally occurring conditions. Minor amounts of Np partition differently from Pu in sediments. The NH₄-acetate treatment, which is designed to liberate trace metals that are loosely adsorbed onto the surfaces of sedimentary materials such as hydrated iron oxides and humic substances, or present at exchangeable sites in clay minerals, mobilized ∼12% of the total Np while Pu levels were below detection. The H₂O₂ treatment, which is designed to liberate trace metals bound to organic matter, mobilized ∼8 and ∼1% of Np and Pu, respectively. These results indicate that a minor portion of the total Np may be affected by environmental conditions that have little or no effect on Pu. Between 7 and 24% of the Pu was observed in treatments designed to liberate Pu and Np that are tightly bound to lithogenic phases or refractory silicates. The ²⁴⁰Pu/²³⁹Pu observed in accessible and refractory fractions ranged between 0.11 and 0.18. With the exception of one sample, the ²⁴⁰Pu/²³⁹Pu isotope ratios measured in the refractory fractions are essentially identical having a mean ratio value of 0.123 ± 0.001 (1σ). The ²⁴⁰Pu/²³⁹Pu ratios provide isotopic evidence that suggests a portion of non-fallout contamination has a refractory nature. The presence of similarly low ²⁴⁰Pu/²³⁹Pu ratios in refractory fractions of sediments from the Ob and Irtysh Rivers suggests the existence of a source of refractory Pu which is consistent with refractory “hot particles” derived from surface tests at the Semipalitinsk test site.     

Fate of polybrominated diphenyl ethers in the environment of the Pearl River Estuary, South China

Ninety-six riverine runoff samples collected at eight major outlets in the Pearl River Delta (PRD), South China, during 2005-2006 were analyzed for 17 brominated diphenyl ether (BDE) congeners (defined as Σ₁₇PBDE). Fourteen and 15 congeners were detected, respectively, in the dissolved and particulate phases. These data were further used to elucidate the partitioning behavior of BDE congeners in riverine runoff. Several related fate processes, i.e. air-water exchange, dry and wet deposition, degradation, and sedimentation, within the Pearl River Estuary (PRE), were examined to estimate the inputs of Σ₁₀PBDE (sum of the target BDE congeners, BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, and -183) and BDE-209 from the PRD to the coastal ocean based on mass balance considerations. The results showed that annual outflows of Σ₁₀PBDE and BDE-209 were estimated at 126 and 940 kg/year, respectively from the PRE to coastal ocean. Besides sedimentation and degradation, the majority of Σ₁₀PBDE and BDE-209 discharged into the PRE via riverine runoff was transported to the coastal ocean.     

Microbial degradation of pharmaceuticals in estuarine and coastal seawater

Microbial degradation rates were measured for 19 pharmaceuticals in estuarine and coastal surface water samples. Antipyrine, carbamazepine, cotinine, sulfamethoxazole, and trimethoprim were the most refractory (half-lives, t_1/2 = 35 to >100 days), making them excellent candidates for wastewater tracers. Nicotine, acetaminophen, and fluoxetine were labile across all treatments (t_1/2 = 0.68-11 days). Caffeine, diltiazem, and nifedipine were also and relatively labile in all but one of the treatments (t_1/2 = 3.5-13 days). Microbial degradation of caffeine was further confirmed by production ¹⁴CO₂. The fastest decay of non-refractory compounds was always observed in more sewage-affected Jamaica Bay waters. Degradation rates for the majority of these pharmaceuticals are much slower than reported rates for small biomolecules, such as glucose and amino acids. Batch sorption experiments indicate that removal of these soluble pharmaceuticals from the water column to sediments is a relatively insignificant removal process in these receiving waters.     

Unusual Salinity Conditions in the Yangtze Estuary in 2006: Impacts of an Extreme Drought or of the Three Gorges Dam?

During the extreme dry year of 2006, abnormal salinity conditions in the Changjiang Estuary of the Yangtze River occurred in partial coincidence with the second impoundment phase of the TGD (Three Gorges Dam). Analysis of discharge observations in the upper reaches of the estuary and of salinity observations in the estuary as a whole reveals that in 2006 salinity was over 100 mg/l during 275 days, over 250 mg/l during 75 days and over 400 mg/l during 48 days. It is well known that this is due to extreme low discharges from the upper catchment area into the estuary. Moreover, large amounts of water consumed along the lower reaches of the Yangtze River can also aggravate the low discharges that lead to stronger saltwater intrusion in the estuary. Of the 75 days that salinity was over 250 mg/l, the low discharge was decreased further by 10 to 20% due to water consumption. The additional impact of the impoundment phase of the TGD (lasting 37 days in autumn) was noticeable only during 7 days in 2006. During that period, the relative contributions of the TGD and the water consumption in the lower reaches of the Yangtze River amounted to 70 and 30%, respectively. It may be concluded that the impact of the second impoundment phase of the TGD on salinity intrusion in the estuary was modest, while the extreme drought of 2006 was the dominant cause.     

Use of multitracers for the study of water mixing in the Paraíba do Sul River estuary

Multitracers were used to study water mixing in the Paraíba do Sul River estuary region in August 2007 (dry season) and March 2008 (rainy season) and to evaluate the reach of the river plume in the direction of the open ocean. Two sampling campaigns were carried out, each in a different season. Based on these results, it was possible to conclude that the multitracers used in this study (salinity, Si, Ba and U, as well as the radium isotopes ²²³Ra, ²²⁴Ra, ²²⁶Ra and ²²⁸Ra) presented satisfactory results toward defining the plume reach and determining the residence time and water-mixing processes in the estuary. A strong correlation was observed between tracers and the distance to the coast. During the low river water discharge period, the riverine water took about 10 days to reach open ocean waters (salinity ∼ 35). During the rainy period this value decreased to 6 days. Based on the radium results, it was possible to calculate diffusion coefficients (K_h) of 23 km² d⁻¹ and 38 km² d⁻¹ for ²²⁴Ra and ²²³Ra, respectively, during the dry season (winter). Values of 65 km² d⁻¹ and 68 km² d⁻¹ for ²²³Ra and ²²⁴Ra, respectively, were found for the rainy period (summer).     

Effects of salinity, DOM and metals on the fate and microbial toxicology of propetamphos formulations in river and estuarine sediment

Toxicity studies tend to use pure pesticides with single organisms. However, natural systems are complex and biological communities diverse. The organophosphate pesticide propetamphos (PPT) has been found exceeding regulatory limits (100 ng L⁻¹) in rivers. We address whether solution properties affect the fate of Analar (Analar-PPT) or industrial PPT (PPT-Ind) propetamphos formulations and whether propetamphos and metal toxicant effects are additive, antagonistic or synergistic? The sorption, desorption, biodegradation and microbial toxicology of Analar-PPT and PPT-Ind were investigated in Conwy River and estuary sediment. Results showed elevated salinity enhanced PPT sorption, while higher salinities increased PPT-Ind retention. Higher dissolved organic matter (DOM) and low salinity slowed Analar-PPT biodegradation (1.9 × 10⁻³ h⁻¹). Analar-PPT and PPT-Ind biodegradation was further reduced by low salinity, high DOM and dissolved Zn and Pb (6.3 × 10⁻⁴ h⁻¹, 1100 h t_½ for Analar-PPT; 7.5 × 10⁻⁴ h⁻¹, 924 h t_½ for PPT-Ind). Toxicity effects of PPT, Zn and Pb in equitoxic ratio were higher for PPT-Ind (4.7 μg PPT-Ind g⁻¹; 581 μg Zn g⁻¹; 395 μg Pb g⁻¹) than for Analar-PPT (34.6 μg PPT g⁻¹; 312 μg Zn g⁻¹; 212 μg Pb g⁻¹) whilst a toxicant ratio 1:100:10 suggested small quantities of Analar-PPT (EC₁₀ = 0.06 μg g⁻¹) affected microbial communities. The combined toxicity effect was more than additive. Thus, industrial formulations and pollutant mixtures should be considered when assessing environmental toxicity.     

长江口邻近海域沉积物中生物硅溶解行为研究

对长江口邻近海域进行调查,分析沉积物中生物硅的空间分布特征,探讨影响生物硅溶解以及保存的因素.结果表明,生物硅含量的平面分布具有近岸高于远海的分布趋势,陆源输入、沉积速率以及水动力条件是影响生物硅在沉积物中埋藏的主要因素.生物硅溶解速率常数随空间以及深度无明显变化规律,间隙水中硅酸盐相对于生物硅溶解度的不饱和程度、有机外壳对生物硅的包裹以及间隙水中Al离子浓度等因素会影响生物硅的溶解进而会影响其在沉积物中的保存和间隙水中硅酸盐浓度的变化.