On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

Validation and in situ application of an automated dissolved nickel monitor for estuarine studies

The validation of a fully automated dissolved Ni monitor for in situ estuarine studies is presented, based on adsorptive cathodic stripping voltammetry (AdCSV). Dissolved Ni concentrations were determined following on-line filtration and UV digestion, and addition of an AdCSV ligand (dimethyl glyoxime) and pH buffer (N-2-hydroxyethylpiperazine-N′-2-ethanesulphonic acid). The technique is capable of up to six fully quantified Ni measurements per hour. The automated in situ methodology was applied successfully during two surveys on the Tamar estuary (south west Britain). The strongly varying sample matrix encountered in the estuarine system did not present analytical interferences, and each sample was quantified using internal standard additions. Up to 37 Ni measurements were performed during each survey, which involved 13 h of continuous sampling and analysis. The high resolution data from the winter and summer tidal cycle studies allowed a thorough interpretation of the biogeochemical processes in the studied estuarine system.

Modeling the effect of ozone loss on photobleaching of chromophoric dissolved organic matter in the St. Lawrence estuary

Temporal trends in total ozone for the St. Lawrence estuary were estimated from ground-based measurements at the NOAA/CMDL station in Caribou, Maine. Linear regression analysis showed that from 1979 to 1999 total ozone has decreased by about 3.3% per decade on an annual basis and ≤6.2% per decade on a monthly basis relative to unperturbed (pre-CFC) levels. The influence of increased ultraviolet-B (280–320 nm) radiation associated with ozone depletion on water column photochemical processes was evaluated by modeling the photobleaching of chromophoric dissolved organic material (CDOM). Linear regression analysis showed small (<0.5% per decade), but statistically significant upward trends in maximum noontime photobleaching rates. Most notably, positive trends in relative rates for May, June, and July, when maximum absolute rates are expected, were predicted. A global model based on TOMS ozone data revealed increases in photobleaching of ≤3% per decade at high latitudes in the Southern Hemisphere. Radiation amplification factors for increases in photochemically weighted UV (280–400 nm) in response to ozone depletion were estimated at 0.1 and 0.08 for photobleaching of CDOM absorbance at 300 and 350 nm, respectively. Application of the laboratory-based model to conditions that more closely resembled those in situ were variable with both overestimation and underestimation of measured rates. The differences between modeled rates and observed rates under quasi-natural conditions were as large or larger than the predicted increases due to ozone depletion. These comparisons suggest that biological activity and mixing play an important, but as yet ill-defined, role in modifying photochemical processes.

Trends in heavy metal levels in the dissolved and particulate phase in the Dutch rhine-meuse (MAAS) delta*

Levels of the heavy metals Cd, Cr, Cu, Pb and Zn, in both the dissolved and particulate phase, were determined in two sampling campaigns in August 1978 and August 1984 in the Dutch Rhine-Meuse (Maas) Delta. Besides the heavy metal concentrations, other important parameters were determined, such as the concentrations of seston, chlorophyll and nutrients. The concentrations of dissolved Cd and of Cd, Pb and Cu in particulate matter were much higher in 1978 than in 1984, especially for Cd. This may be due to the strict regulations implemented in Germany to reduce the pollution of natural waters by heavy metals. The correlation between the high Cd content and the chlorophyll content is explained by the binding of Cd to living and dead organisms. The distribution of the metals between the dissolved and the particulate phase, indicated by the distribution quotient Kd , increases from low values of Kd for Cu and Zn, to higher values for Cd and Cr, and the highest values for Pb. The differences are explained by various binding forms of each of these metals in natural waters

Model analysis of dissolved inorganic phosphorus exports from the Yangtze river to the estuary

In this paper, we estimate the inputs of phosphorus (P) to the Yangtze River Basin and exports of dissolved inorganic phosphorus (DIP) from the river to the estuary for the period 1970-2003, by using the global NEWS-DIP model. Modeled DIP yields range from 2.5 kg P km(-2) yr(-1) in 1970 to 4.6 kg P km(-2) yr(-1) in 1985, and then dramatically increase to 14.1 kg P km(-2) yr(-1) in 2003. No significant difference between the modeled and measured values at the level of P = 0.05 is observed. The study also demonstrates variable source contributions of P to the modeled DIP during the period 1970-2003. Point sewage P input accounted for approximately 100% in the period 1970-1985 and substantially decreased to 24.8% in 2003. Chemical fertilizer contributed 25.4% of DIP yields in 1986 and increased continuously to 50.3% in 2003, while a stable trend in manure P contribution averaging 22.9% of DIP yields was shown in the same period. The study concludes that P inputs to the Yangtze River Basin and the river DIP export to the estuary have substantially increased during the study period consequence to human pressure.

A Simple and Inexpensive Method for Fabrication of Ultramicroelectrode Array and Its Application for the Detection of Dissolved Oxygen

Herein, we report a simple and inexpensive way for fabrication of ultra microelectrode arrays (UMEAs) and the relative characterization methods. The fabrication of UMEAs involves only a few steps of handwork. Since only metal wires and epoxy are used through the fabrication process, it is supposed to be a quite straightforward method for preparing UMEAs. A dissolved oxygen (DO) sensor based on UMEAs was constructed.

Nafion-graphene nanocomposite film as enhanced sensing platform for ultrasensitive determination of cadmium

In this work, an ultrasensitive platform for the detection of cadmium (Cd2+) combining the nafion-graphene nanocomposite film with differential pulse anodic stripping voltammetry (DPASV) analysis was presented. It is found that this sensing platform exhibits enhanced response to the determination of the Cd2+ and has been used to determine the Cd2+ in real sample with good recovery.