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.     

不同季节辽河口营养盐的河口混合行为

分别于2010年4、7、11月对大辽河口水域进行了3个航次的调查,测定了水体中各形态营养盐的浓度.结果表明,各形态氮、磷浓度的季节变化明显.PO3-4-P、DOP、DTP和TP平均含量的季节分布相似:均为4月最高,11月次之,7月最低;而PP平均含量由大到小依次为11、4、7月.NO-3-N、NO-2-N的含量为7月最高,4月最低;NH+4-N、DON、PN的含量为4月最高,7月最低.4月NH+4-N为TN的主要存在形态,而7、11月NO-3-N为N的主要存在形态.NO-3-N、DIN、TN在3个季节的河口混合过程中均呈保守性;而NO-2-N、NH+4-N、DON在4、11月也是保守性的,但在7月为非保守性,在河口内部存在添加源.3个季节大辽河口水域的硅酸盐均呈现保守行为,11月平均含量最高,4月最低.     

2012年夏季长江口颗粒有机碳、氮分布特征及其来源

基于2012年8月对长江口及其邻近海区的调查资料,分析了长江口夏季颗粒有机碳(particulate organic carbon,POC)、颗粒氮(particulate nitrogen,PN)的空间分布特征及其与环境因子的关系,并结合C/N摩尔比值和叶绿素a(chlorophyll a,Chl a)探讨了POC的主要来源及浮游植物的贡献.结果表明,2012年夏季长江口POC的质量浓度范围在0.68~34.80mg·L-1之间,均值为3.74 mg·L-1;PN的质量浓度范围为0.03~9.13 mg·L-1,均值0.57 mg·L-1,二者浓度均表现为底层高于表层.POC和PN平面分布相似,高值区均出现在口门附近和调查海区西南部,并向外海浓度迅速降低,整体呈现近岸高、远岸低的趋势,与总悬浮物(total suspended matter,TSM)的平面分布规律基本相同;POC与PN间呈极显著正相关,表明二者具有高度的同源性.POC、PN与TSM、化学需氧量(chemical oxygen demand,COD)间均呈现极显著线性正相关,而与盐度(salinity,S)和Chl a的相关关系较弱,表明POC和PN的分布受陆源输入的影响较大,浮游植物生产不是该水域颗粒有机碳、氮的主要来源.C/N摩尔比和POC/Chl a法分析表明夏季长江口POC主要为陆源,有机碎屑是POC的主要存在形式.定量估算结果表明,浮游植物生物量对夏季长江口表层POC的平均贡献率仅为2.54%,非生命POC占绝对优势地位.     

珠江河口水域有机磷农药水生生态系统风险评价

通过风险商法和概率风险法评价了珠江河口水域中甲拌磷、敌敌畏及乙拌磷等9种有机磷农药对硅藻、水蚤及糠虾等8种水生生物的生态风险.风险商法评价结果表明,9种有机磷农药混合物总风险商为:糠虾处于高风险中水平,水蚤和摇蚊在中等风险水平,硅藻、牡蛎、鲤鱼、鲶鱼和鳗鱼均处于低风险水平;甲拌磷对风险值的贡献最大,且对每种生物都有影响.概率风险法结果表明,以HC5为参考值评估总风险商时,95%置信水平下的HC5比50%置信水平的HC5保守,50%置信水平的HC5中乐果的HC5最大,毒死蜱的最小;丰水期9种有机磷农药混合物总风险比枯水期农药混合物总风险大,甲拌磷对总风险贡献最大.单一污染物的概率风险表明,甲拌磷和乙拌磷对珠江河口水域中10%以上的生物都有危害;而9种有机磷农药混合物的概率风险表现为:丰水期大于枯水期,均大于5%,说明超过了保护95%生物的安全阈值.     

Influences of sediment dessication on phosphorus transformations in an intertidal marsh: formation and release of phosphine

This study investigated the effects of sediment dewatering on the phosphorus transformations concerning about the production and emission of phosphine in the intertidal marsh of the Yangtze Estuary. The concentrations of matrix-bound phosphine ranged from 18.62-72.53 ng kg⁻¹ and 31.14-61.22 ng kg⁻¹ within the August and January exposure incubations, respectively. The responses of matrix-bound phosphine concentrations to sediment dessication demonstrate that the production (or accumulation) of matrix-bound phosphine significantly increased with water loss at the start of the emersion incubations. However, further dehydration inhibited the formation of matrix-bound phosphine in sediments. The significant correlations of matrix-bound phosphine with the organic-P bacteria abundance and alkaline phosphatase activities implicate that the production of matrix-bound phosphine within the dessication incubations was linked closely to the microbial decomposition of organic P. The emissions of phosphine generally decreased with sediment dewatering, with the fluxes of 7.51-96.73 ng m⁻² h⁻¹ and 5.34-77.74 ng m⁻² h⁻¹ over the exposure incubations of both August and January, respectively. Also, it is observed that the releases of phosphine during the entire exposure periods were affected not only by its production but also by sediment water and redox conditions.