Managing the Use of Copper-Based Antifouling Paints

Copper is the biocide of choice for present-day antifouling (AF) paints. It is also a major source of copper loading in to the marine environment and, as such, might cause local copper levels to exceed water quality criteria. The present study is multifaceted and looks into the overall impact of copper-based AF paints on copper concentrations along a 64-km stretch of the Indian River Lagoon and at Port Canaveral, Florida. This preliminary study is one of the first to outline issues and present background evidence on the current status of copper and copper-based AF usage in Florida and to address the need for management. Previous measurements of copper levels in these waters show a history of copper contamination close to marinas, boatyards, and at Port Canaveral that often exceed state and federal water quality standards. Further, we estimate that the total annual copper input into the Indian River Lagoon is between 1.7 tons/year (sailboats) and 2.1 tons/year (powerboats) from boats in 14 marinas. We estimate the copper input into Port Canaveral to be about 1.4 tons/year from seven cruise ships. A brief survey of marina operators and boat owners revealed attitudes and practices associated with AF paint usage that ranged from excellent to inferior. Management recommendations are made for a proactive approach to improving AF paint selection and application, assessing the environmental status of copper, and redefining existing management practices for sustainable AF paint usage and environmental health.     

Assessing the long-term supply risks for mineral raw materials—a combined evaluation of past and future trends

This paper develops a method for identifying and assessing long-term supply risks for mineral raw materials. The method is based on a combined evaluation of past and future supply and demand trends. By analysing raw material boom and bust cycles over the past 50 years, we have quantified indicators and defined benchmarks for identifying critical market situations. By applying the method, risks for supply shortage may be identified at an early stage. In addition, a numerical evaluation model has been developed for better comparison between various mineral raw materials. Compared to other assessment methods this method uses specific benchmarks for each raw material to better assess supply risks. The method is embedded within a systematic and comprehensive analytical approach.     

Interactions Among the Copper Species and Forms in Sea Water/Sediments and Copper Bioaccumulation in Oysters

Abstract

Earlier papers indicated that the first incident of green discoloration in oysters (Crassostrea gigas) and the mass mortality observed in 1986 along the Taiwan Erhjin Chi coastal area were caused by the higher contents of total copper and copper species (mainly bioavailable and free ion) in sea water. the copper in sea water would be sorbed by suspended matter and transferred to sediments, and the copper in the sediments would also be desorbed to sea water. Processes of copper adsorption and desorption are the major factors influencing the contents of total copper and copper species in sea water and sediments. in this study, the Erhjin Chi sediments were mixed with sea water by a shaker technique. When the mixture was shaken for one hour, analogous to tidal mixing in estuaries, only copper desorption from sediments was observed. If the shaking time is increased for more than 3 hours, the copper released from the sediments was resorbed to the remaining solid phases. the higher the contents of mud (91.71%) and total copper (701 mg kg^?1) in sediments, the higher the copper desorption rate (1.86 ppm hr^?1) and copper adsorption rate (0.50 ppm hr^?1) were observed. in sediments containing lower mud (0.80%) and lower copper (43.5 mg kg^?1), the copper desorption and adsorption rates were 0.83 ppm hr^?1 and 0.22 ppm hr^?1, respectively. the interactions among the total copper and copper species in sea water and sediments, chemical and ecological parameters, and copper bioaccumulation in oysters in the Erhjin Chi estuarine and coastal area are also discussed.     

DDTC—TX—100胶束增溶直接光度法测定水中低含量铜

ＴｒｉｔｏｎＸ１００对ＤＤＴＣ（二乙基二硫代氨基甲酸钠）与铜反应生成的络合物Ｃｕ（ＤＤＴＣ）２有增溶增敏作用，建立了低含量铜直接光度测定法。操作简便快速，选择性、精密度和回收率均较好，相对标准偏差为０８％～４３％，回收率为９６％～１０６％，摩尔吸光系数ε＝６４×１０３Ｌ／（ｍｏｌ·ｃｍ     

Entry and toxicity of organic pesticides and copper in vineyard streams: Erosion rills jeopardise the efficiency of riparian buffer strips

The present study was performed to characterise in-stream pesticide exposure within the Palatinate vineyard region in south-west Germany, evaluate the influence of buffer strip widths and identify mitigation measures for the relevant entry pathways. In-stream water and sediment samples that were taken at nine sampling sites of different buffer widths following intense rainfall, and edge-of-field runoff that were sampled in erosion rills were analysed regarding 28 active ingredients of pesticides including copper. In-stream samples contained a mix of 8 ± 4 pesticide compounds, resulting in total pesticide concentrations of 1.4-8.9 μg l⁻¹ for water and 16-670 μg kg⁻¹ dw for sediment. Following an exceptional rainfall event with a previous 34-day drought period, pesticide concentrations reached 7.0-83.4 μg l⁻¹. Fungicides were the most important pesticides found and were significantly correlated with the pesticide application frequency and rate. The calculated toxicity values per sample (TU_max) indicated that both organic pesticides and copper concentrations likely cause ecotoxicological effects in the field. The buffer strip width was of little importance for pesticide in-stream concentrations because pesticide entry occurred mainly via the field path network and erosion rills. Pesticide in-stream concentrations were significantly and positively correlated with the concentrations detected in erosion rills (R² = 0.56). As possible risk mitigation measures, we suggest the implementation of grassed field paths and vegetated ditches or wetlands.     

Copper complexation by tannic acid in aqueous solution

The speciation of titrated copper in a dissolved tannic acid (TA) solution with an initial concentration of 4 mmol organic carbon (OC)/l was investigated in a nine-step titration experiment (Cu/OC molar ratio = 0.0030–0.0567). We differentiated between soluble and insoluble Cu species by 0.45 μm filtration. Measurements with a copper ion selective electrode (ISE) and diffusive gradients in thin films (DGT) were conducted to quantify unbound Cu(II) cations (‘free’ Cu) and labile soluble Cu complexes. For the DGT measurements, we used an APA hydrogel and a Chelex 100 chelating resin (Na form). Insoluble organic Cu complexes (>0.45 μm) was the dominant Cu species for Cu/OC = 0.0030–0.0567 with a maximum fraction of 0.96 of total Cu. At Cu/OC > 0.0100, Cu-catalysed degradation of aggregate structures resulted in a strong increase of free Cu and (labile) soluble Cu complexes with a maximum fraction of 0.28 and 0.32 of total Cu, respectively. Labile (i.e. DGT-detectable) soluble Cu complexes had a relatively high averaged diffusion coefficient (D) in the APA hydrogel (3.50 × 10⁻⁶– 5.58 × 10⁻⁶ cm² s⁻¹).     

Metal bioaccumulation and metallothionein concentrations in larvae of Crassostrea gigas

Larval stages of bivalve molluscs are highly sensitive to pollutants. Oysters from a hatchery from Normandy (English Channel) were induced to spawn, and fertilized eggs were exposed to copper or cadmium for 24 h. Metal accumulation (from 0.125 to 5 microg Cu L(-1) and from 25 to 200 microg Cd L(-1)) and MT concentrations were measured in larvae. Compared to controls, larvae accumulated copper and cadmium with an increase in MT concentrations particularly with cadmium (i.e. 130.96 ng Cu (mg protein)(-1) and 12.69 microg MT (mg protein)(-1) at 1 microg Cu L(-1) versus 23.19 ng Cu (mg protein)(-1) and 8.92 microg MT (mg protein)(-1) in control larvae; 334.3 ng Cd (mg protein)(-1) and 11.70 microg MT (mg protein)(-1) at 200 microg Cd L(-1) versus 0.87 ng Cd (mg protein)(-1) and 4.60 microg MT (mg protein)(-1) in control larvae). Larvae were also obtained from oysters of a clean area (Arcachon Bay) and a polluted zone (Bidassoa estuary) and exposed to copper in the laboratory, their MT concentration was measured as well as biomarkers of oxidative stress. Biomarker responses and sensitivity to copper for the larvae from Arcachon oysters were higher than for those from Bidassoa.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

Analysis of chromium and copper by cathodic stripping voltammetry with mixed ligands

Cathodic adsorptive stripping voltammetry is one of the most sensitive analytical methods for ultratrace analysis. The detection limit is usually lower than 10⁻⁹ mol/L. Most adsorptive stripping procedures have been focused on the one ligand/one analyte approach. In order to reduce analysis time and sample volume, the possibility of simultaneously determining several metals by cathodic stripping voltammetry using a mixture of ligands was explored, e.g., by Colombo and van den Berg (1997). Here, we describe a new procedure for quantifying chromium and copper using 2,2′-bipyridine and 8-hydroxyquinoline (oxine). The effect of various operational parameters such as buffer type, ligand concentration, potential and time collection were assessed and optimized. Possible interferences by trace metals and organic matter were also investigated. Applicability for fresh water is illustrated. Electronic Publication     

Cu and Cd removal from wastewater by a microalloyed aluminium composite

We studied the removal of cadmium and copper from industrial wastewaters by a microalloyed aluminium composite. The composite was highly efficient, resulting in water concentrations of cadmium and copper below the maximal allowed concentrations for drinking water. Moreover, our results show that the removal mechanism is mainly based on reduction and coprecipitation, since Cd and Cu were removed from the wastewater in reduced forms as metals and hydroxides.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic