University of Geneva, Sciences II, 30 Quai E.-Ansermet, 1221, Geneva 4, Switzerland.
University of Geneva, Sciences II, 30 Quai E.-Ansermet, 1221, Geneva 4, Switzerland; CIIMAR, Avenida General Norton de Matos, S/N, 4450-208, Matosinhos, Portugal.
J Environ Manage. 2022 Sep 1;317:115375. doi: 10.1016/j.jenvman.2022.115375. Epub 2022 Jun 7.
The water column of harbors contains significant amounts of (priority) hazardous trace metals that may be released into coastal areas of high societal and economic interests where they may disturb their fragile equilibria. To deepen our understanding of the processes that influence the transport of the various metal fractions and allow for a more rigorous environmental risk assessment, it is important to spatially monitor the relevant chemical speciation of these metals. It is of particular interest to assess their so-called dynamic fraction, which comprises the dissolved chemical forms that are potentially bioavailable to living organisms. In this study this was achieved in the Genoa Harbor (NW Italy) for copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) by applying a multi-method approach. For the first time in this system the dynamic fractions of the target metals (Cu, Cd, Pb, Zn) were observed in real-time on-board by voltammetry using innovative electrochemical sensing devices. Trace metals in the operationally defined dissolved <0.2 μm and <0.02 μm fractions were equally quantified through sampling/laboratory-based techniques. The obtained results showed a clear spatial trend for all studied metals from the enclosed contaminated part of the harbor towards the open part. The highest Cu and Cd fractions were found in the inner part of the harbor while the highest Pb fraction was found in the open part. The proportion of Zn was negligible in the sampled area. Small and coarse colloids were involved in Cu, Cd and Zn partitioning while only coarse colloids played an important role in Pb partitioning. The determined concentrations were compared to the Environmental Quality Standards (EQS) established by the EU and those determined by the Australia and New Zealand to trigger for 99 and 95% species protection values. The results of this work allow us to highlight gaps in the EQS for which metal concentration thresholds are excessively high or non-existent and should urgently be revised. They also reflect the need to quantify the potentially bioavailable fraction of hazardous trace metals instead of just their total dissolved concentrations. The data support the establishment of environmental quality standards and guidelines based on realistic risk assessment to protect aquatic life and resources and ultimately human health.
港口水体内含有大量（优先考虑的）有害痕量金属，这些金属可能会释放到具有高社会和经济利益的沿海地区，从而扰乱这些地区脆弱的生态平衡。为了更深入地了解影响各种金属形态传输的过程，并进行更严格的环境风险评估，对这些金属的相关化学形态进行空间监测非常重要。评估它们所谓的动态分数尤为重要，因为该分数包含了对生物具有潜在生物利用度的溶解化学形式。在本研究中，通过应用多方法方法，在意大利西北部的热那亚港（Genoa Harbor）对铜（Cu）、铅（Pb）、镉（Cd）和锌（Zn）进行了相关研究。这是首次在该系统中，通过使用创新的电化学传感装置，通过伏安法实时在线观测到目标金属（Cu、Cd、Pb、Zn）的动态分数。通过采样/实验室技术，同样定量了操作定义的溶解<0.2μm 和<0.02μm 分数中的痕量金属。获得的结果表明，在所研究的所有金属中，从港口受污染的封闭部分到开放部分都存在明显的空间趋势。在港口内部发现了最高的 Cu 和 Cd 分数，而在开放部分发现了最高的 Pb 分数。在所采样区域中 Zn 的比例可以忽略不计。Cu、Cd 和 Zn 的分配涉及小而粗的胶体，而只有粗胶体在 Pb 的分配中起重要作用。所确定的浓度与欧盟制定的环境质量标准（EQS）以及澳大利亚和新西兰确定的 EQS 进行了比较，以触发 99%和 95%物种保护值。这项工作的结果使我们能够突出 EQS 中的差距，这些差距导致金属浓度阈值过高或不存在，急需进行修订。它们还反映了量化有害痕量金属的潜在生物利用分数的必要性，而不仅仅是其总溶解浓度。这些数据支持根据现实风险评估建立环境质量标准和指南，以保护水生生物和资源，并最终保护人类健康。
