Importance of heterocylic aromatic compounds in monitored natural attenuation for coal tar contaminated aquifers: A review

NSO heterocycles (HET) are typical constituents of coal tars. However, HET are not yet routinely monitored, although HET are relatively toxic coal tar constituents. The main objectives of the study is therefore to review previous studies and to analyse HET at coal tar polluted sites in order to assess the relevance of HET as part of monitored natural attenuation (MNA) or any other long-term monitoring programme. Hence, natural attenuation of typical HET (indole, quinoline, carbazole, acridine, methylquinolines, thiophene, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, methylbenzofurans, dimethylbenzofurans and xanthene) were studied at three different field sites in Germany. Compound-specific plume lengths were determined for all main contaminant groups (BTEX, PAH and HET). The results show that the observed plume lengths are site-specific and are above 250m, but less than 1000m. The latter, i.e. the upper limit, however mainly depends on the level of investigation, the considered compound, the lowest measured concentration and/or the achieved compound-specific detection limit and therefore cannot be unequivocally defined. All downstream contaminant plumes exhibited HET concentrations above typical PAH concentrations indicating that some HET are generally persistent towards biodegradation compared to other coal tar constituents, which results in comparatively increased field-derived half-lives of HET. Additionally, this study provides a review on physicochemical and toxicological parameters of HET. For three well investigated sites in Germany, the biodegradation of HET is quantified using the centre line method (CLM) for the evaluation of bulk attenuation rate constants. The results of the present and previous studies suggest that implementation of a comprehensive monitoring programme for heterocyclic aromatic compounds is relevant at sites, if MNA is considered in risk assessment and for remediation.     

Assessing the recovery of lakes in southeastern Canada from the effects of acidic deposition

Reductions in North American sulfur dioxide (SO2) emissions promoted expectations that aquatic ecosystems in southeastern Canada would soon recover from acidification. Only lakes located near smelters that have dramatically reduced emissions approach this expectation. Lakes in the Atlantic provinces, Quebec and Ontario affected only by long-range sources show a general decline in sulfate (SO4(2-)) concentrations, but with a relatively smaller compensating increase in pH or alkalinity. Several factors may contribute to the constrained (or most likely delayed) acidity response: declining base cation concentrations, drought-induced mobilization of SO4(2-), damaged internal alkalinity generation mechanisms, and perhaps increasing nitrate or organic anion levels. Monitoring to detect biological recovery in southeastern Canada is extremely limited, but where it occurs, there is little evidence of recovery outside of the Sudbury/Killarney area. Both the occurrence of Atlantic salmon in Nova Scotia rivers and the breeding success of Common Loons in Ontario lakes are in fact declining although factors beyond acidification also play a role. Chemical and biological models predict that much greater SO2 emission reductions than those presently required by legislation will be needed to promote widespread chemical and latterly, biological recovery. It may be unrealistic to expect that pre-industrial chemical and biological conditions can ever be reestablished in many lakes of southeastern Canada.     

Decreased acid deposition and the chemical recovery of Killarney,Ontario, lakes

Lakes in Killarney Park near Sudbury, Ontario, Canada, have shown dramatic water quality changes including general increases in pH and alkalinity, and decreases in SO4(2-), base cations and metals. While some lakes have recovered to pH > 6.0, many are still highly acidic despite decades of improvement. Very high historical S deposition related to emissions from the Sudbury metal smelters dominated the acidification process in this region. However, since the implementation of substantial S emission controls (90%) at the smelters, the Sudbury emissions are no longer the major source of S deposition in the Sudbury area. Wet deposition of SO4(2-) and SO4(2-) concentrations in lakewaters at Killarney now approach values in the Dorset, Ontario, area, about 200 km from Sudbury. This suggests that the S deposition to the Killarney area is now primarily from long-range transport, not from local sources. Studies of Killarney lakes are revealing the complex nature of the chemical recovery process. As lake acidity decreases, other changes including decreased Ca2+ concentrations, increased transparency, and altered thermal regimes may potentially affect some of these ecosystems. It is clear that continuing assessments of the recovery of Killarney lakes, within a multiple-stressor framework, are needed.     

酸沉降作用的降低和安大略省基拉尼湖泊的化学恢复

毗邻加拿大安大略省萨德伯里市的基拉尼公园中的湖泊都表现出明显的水质变化,其中包括pH值和碱度的普遍增加,SO2- 4、碱基阳离子和金属浓度的减少.经过数十年的改善,尽管一些湖泊的pH值已经大于6,但仍有许多湖泊的湖水酸度却一直很高.过去,萨德伯里金属冶炼厂排放引起的过高的硫沉降左右了这一地区的酸化过程.然而,自从冶炼厂的硫排放被严格控制之后(排放量降低了90%),萨德伯里地区的硫排放就不再是该地区最主要的硫沉降源了.目前,基拉尼地区的SO2- 4湿沉降和湖水中SO2- 4浓度已经十分接近约200km外的安大略省多赛特地区,这就表明基拉尼地区的硫沉降现在主要来自于长距离传输,而不是当地污染源.对基拉尼湖泊的研究揭示了化学恢复过程的复杂本质.一旦湖水的酸度降低,就会引起一系列的变化,包括Ca2+浓度的减少,透明度增加和热力学状态改变.这些变化可能会潜在地影响一些生态体系.因此很明显需要对基拉尼湖泊的恢复在多胁迫因子的框架内继续进行评价.     

Acute and chronic effects of nano- and non-nano-scale TiO2 and ZnO particles on mobility and reproduction of the freshwater invertebrate Daphnia magna

Among the emerging literature addressing the biological effects of nanoparticles, very little information exists, particularly on aquatic organisms, that evaluates nanoparticles in comparison to non-nanocounterparts. Therefore, the potential effects of nano-scale and non-nano-scale TiO₂ and ZnO on the water flea, Daphnia magna, were examined in 48-h acute toxicity tests using three different test media, several pigment formulations – including coated nanoparticles – and a variety of preparation steps. In addition, a 21-d chronic Daphnia reproduction study was performed using coated TiO₂ nanoparticles. Analytical ultracentrifugation analyses provided evidence that the nanoparticles were present in a wide range of differently sized aggregates in the tested dispersions. While no pronounced effects on D. magna were observed for nano-scale and non-nano-scale TiO₂ pigments in 19 of 25 acute (48-h) toxicity tests (EC50 > 100 mg L⁻¹), six acute tests with both nano- and non-nano-scale TiO₂ pigments showed slight effects (EC10, 0.5–91.2 mg L⁻¹). For the nano-scale and non-nano-scale ZnO pigments, the acute 48-h EC50 values were close to the 1 mg L⁻¹ level, which is within the reported range of zinc toxicity to Daphnia. In general, the toxicity in the acute tests was independent of particle size (non-nano-scale or nano-scale), coating of particles, aggregation of particles, the type of medium or the applied pre-treatment of the test dispersions. The chronic Daphnia test with coated TiO₂ nanoparticles demonstrated that reproduction was a more sensitive endpoint than adult mortality. After 21 d, the NOEC for adult mortality was 30 mg L⁻¹ and the NOEC for offspring production was 3 mg L⁻¹. The 21-d EC10 and EC50 values for reproductive effects were 5 and 26.6 mg L⁻¹, respectively. This study demonstrates the utility of evaluating nanoparticle effects relative to non-nano-scale counterparts and presents the first report of chronic exposure to TiO₂ nanoparticles in D. magna.     

酸化湖泊水生生物恢复的理论框架构建

在欧洲和北美广大地区,随着大气硫沉降的减少,地表水体酸度正在逐渐降低,但是对水质改善的生态响应过程却依然扑朔迷离.有些湖泊和河流的生物正在恢复,有些水体的生物并没有得到恢复.为理解这些生物响应的差异,有利于酸雨问题的有效管理,我们需要对下面2个问题有清晰的认识:①生物群落恢复所必须经历的生态步骤;②倘若恢复受阻,从哪里着手对恢复进程实施干预,如何干预.本文通过构建一套理论框架来回答上述问题.第一层框架是基于生态学考虑而构建的,通过决策树来反映生态恢复进程中必须经历的若干步骤,步骤之间则通过管理工具或对瓶颈的响应来连接.水质不佳,移生生物供给不足以建群,以及群落水平上对恢复动态变化的阻碍等等都可能成为恢复的瓶颈所在.第二层框架则是基于管理层次来构建的,为了克服瓶颈,框架指明从哪里着手对恢复进程实施干预,为建模来进一步将框架具体化,需要做哪些研究.一旦我们可以用模型来预测酸化水体生态恢复的速率和程度,对硫排放减少带来的效益评价就变得简单起来.而这些模型的构建需要充分认识恢复进程中的生态步骤.本文提出的理论框架将有助于我们朝这个目标迈进.     

Reconstruction of centuries-old Daphnia communities in a lake recovering from acidification and metal contamination

Paleolimnological and molecular genetic techniques were combined to reconstruct the long-term patterns in Daphnia community composition in Hannah Lake--a lake recovering from industrial acidification, metal contamination and faunal extirpation. Like many zooplankters, Daphnia produce diapausing eggs that can remain viable for decades and even over a century. Yet, the appearance of D. mendotae in Hannah Lake during the last two decades is likely the outcome of dispersal from other nearby lakes, not by colonization from the sediment egg-bank. Our genetic tests using PCR, SSCP and sequencing indicate that D. mendotae diapausing eggs are absent within the sediment record of the previous 250 years and that, prior to metal smelting operations in the region, the community was dominated by D. pulicaria. This species shift following the lake's chemical restoration is consistent with earlier historical changes in lake acidity. Environmental fluctuations may have governed community composition throughout Hannah Lake's more ancient past. Extending this molecular-paleolimnological approach to other lakes should help develop more accurate formulations of the biological recovery process.