Copper speciation survey from UK marinas, harbours and estuaries

The use of copper in antifouling paints has increased in the UK in the last 20 years as TBT and several other organic biocides have been phased out. To assess the probable impact of copper on estuarine systems a survey was undertaken to measure the different fractions of copper present in the water column at current usage. The different fractions measured were; labile copper, (LCu) considered as both the free copper ions and inorganically bound copper, the total dissolved copper (TDCu) present, and the difference between them taken as the organically bound likely non-toxic copper fraction. The survey considered sites with different levels of boat use, namely marinas, harbours and estuaries, differing physical parameters of suspended and dissolved organic matter, different seasons of the year and different depths in the water column all of which control speciation behaviour. Suspended particulate matter (SPM) values were measured at all sites and increased from West to East coast locations (5.7-34.4 mg/l). Dissolved organic matter (DOM) values ranged from 0.58 to 2.2mg/l C. The total dissolved copper concentrations ranged from 0.30 to 6.68 microg/l, with labile fraction ranging from 0.02 to 2.69 microg/l, and most labile copper concentrations below 1 microg/l. None of the yearly mean copper measurements exceeded the 76/464/EEC EQS of 5 microg/l. Of the 306 measurements, only one dissolved copper value in one season was above 5 microg/l. This ratio of labile to total copper was between 10 and 30%. The results from this survey suggest that if toxicity of copper is due to the labile fraction then using the total dissolved copper concentrations as an indicator of impact overestimate the risk by a factor of four times.     

Biodiversity of rocky intertidal benthic communities associated with copper mine tailing discharges in northern Chile

Copper mine tailings have been discharged around the city of Chanaral, in northern Chile, for more than 60 years. This report summarizes a 17-month long monitoring study of species richness and biodiversity at five intertidal sites around the point of the tailing discharge. Total dissolved copper in sites close to the point of discharge varied between 8.72 microg/l and 34.15 microg/l, showing that there has not been a significant reduction since 1994. However, species richness has increased, suggesting a possible recovery of the system. While diversity of sessile organisms correlates negatively with dissolved copper, diversity of mobile invertebrates did not correlate with the metal concentration. To explain the observed results we discuss the role of algal turf interference on the distribution of mobile invertebrates at reference sites, a top-down effect caused by the absence of carnivores at impacted sites, and an avoidance strategy by some species to reduce their contact with contaminated seawater.     

Assessing the influence and distribution of shrimp pond effluent in a tidal mangrove creek in north-east Australia

Effluent from a land based shrimp farm was detected in a receiving creek as changes in physical, chemical and biological parameters. The extent and severity of these changes depended on farm operations. This assessment was conducted at three different stages of shrimp-pond maturity, including (1) when the ponds were empty, (2) full and (3) being harvested. Methods for assessing farm effluent in receiving waters included physical/chemical analyses of the water column, phytoplankton bioassays and nitrogen isotope signatures of marine flora. Comparisons were made with an adjacent creek that served as the farms intake creek and did not directly receive effluent. Physical/chemical parameters identified distinct changes in the receiving creek with respect to farm operations. Elevated water column NH(4)(+) (18.5+/-8.0 microM) and chlorophyll a concentrations (5.5+/-1.9 microg/l) were measured when the farm was in operation, in contrast to when the farm was inactive (1.3+/-0.3 microM and 1.2+/-0.6 microg/l, respectively). At all times, physical/chemical parameters at the mouth of the effluent creek, were equivalent to control values, indicating effluent was contained within the effluent-receiving creek. However, elevated delta(15)N signatures of mangroves (up to approximately 8 per thousand) and macroalgae (up to approximately 5 per thousand ) indicated a broader influence of shrimp farm effluent, extending to the lower regions of the farms intake creek. Bioassays at upstream sites close to the location of farm effluent discharge indicated that phytoplankton at these sites did not respond to further nutrient additions, however downstream sites showed large growth responses. This suggested that further nutrient loading from the shrimp farm, resulting in greater nutrient dispersal, will increase the extent of phytoplankton blooms downstream from the site of effluent discharge. When shrimp ponds were empty water quality in the effluent and intake creeks was comparable. This indicated that observed elevated nutrient and phytoplankton concentrations were directly attributable to farm operations.     

Effects of antifouling paint components (TBTO,copper and triazine) on the early development of embryos in cod (Gadus morhua L.)

To assess the risk of antifoulant use to the commercially important cod (Gadus morhua L.), fertilised cod eggs were exposed to triazine, copper and TBTO singly or combined in laboratory tests with running seawater. At the highest tested concentrations (11.5 microg Cu l(-1); 5 microg TBTO l(-1)) larval mortality was increased. The highest concentration of triazine (40 microg l(-1)) did not cause any significant mortality. Fertilised eggs that had been exposed to all the three chemicals singly for five days showed a higher buoyancy than the controls. No synergistic or antagonistic effects were indicated. Embryos/larvae exposed to 0.004-0.8 microg TBTO l(-1) did not show any changed respiration compared to the controls after hatching. It is concluded that existing known field concentrations of the three antifoulants are hardly expected to cause detectable effects on fish embryonic/larval development.     

Trace metals associated with deep-sea tailings placement at the Batu Hijau copper–gold mine,Sumbawa, Indonesia

The Batu Hijau copper–gold mine on the island of Sumbawa, Indonesia operates a deep-sea tailings placement (DSTP) facility to dispose of the tailings within the offshore Senunu Canyon. The concentrations of trace metals in tailings, waters, and sediments from locations in the vicinity of the DSTP were determined during surveys in 2004 and 2009. In coastal and deep seawater samples from Alas Strait and the South Coast of Sumbawa, the dissolved concentrations of Ag, As, Cd, Cr, Hg, Pb and Zn were in the sub μg/L range. Dissolved copper concentrations ranged from 0.05 to 0.65 μg/L for all depths at these sites. Dissolved copper concentrations were the highest in the bottom-water from within the tailings plume inside Senunu Canyon, with up to 6.5 μg Cu/L measured in close proximity to the tailings discharge. In general, the concentrations of dissolved and particulate metals were similar in 2004 and 2009.     

Protective effect of phospholipid hydroperoxide glutathione peroxidase (PHGPx) against lipid peroxidation in mussels Perna perna exposed to different metals

Levels of antioxidant defenses and lipid peroxidation were evaluated in mussels exposed to lead (200 mg/l), iron (500 microg/l), cadmium (200 microg/l) and copper (40 microg/l), for 12, 24, 72 and 120 h. Glutathione S-transferase (GST) activity was unchanged with all treatments. Catalase (CAT) increased after 120 h of exposure to all metals. Mussels exposed to Cd for 12 h, and to Cu and Fe for 120 h had increased lipid peroxidation, which might be associated to decreased levels of reduced glutathione (GSH) and glutathione peroxidase (GPx) activity. Pb exposure caused GSH depletion after 12 h and increased GPx activity after 120 h. Negative correlations were observed between the enzyme phospholipid hydroperoxide glutathione peroxidase (PHGPx) and malonaldehyde (MDA) levels after Fe and Cu exposure, indicating a protective role of PHGPx against lipid peroxidation, and suggesting the use of this enzyme as a new potential biomarker of toxicity associated with contaminant exposure in mussels.     

Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia

Concentrations of dissolved metals (Cd, Cu, Ni, Mn and Zn) were determined for summer and winter, under low-flow conditions in Port Jackson, a microtidal, well-mixed estuary in south-east Australia. Mean concentrations of Cd (0.04+/-0.02 microg/l), Ni (0.86+/-0.40 microg/l), Mn (20.0+/-25 microg/l) and Zn (6.47+/-2.0 microg/l) were below water quality guidelines. Concentrations of Cu (1.68+/-0.37 microg/l), however, slightly exceeded recommended values. Dissolved Ni and Mn behaved mostly conservatively, whereas Cd, Cu and Zn showed mid-estuarine maxima. Peaks in Cd, Cu and Zn concentrations were located in the upper estuary, independent of the salinity and suspended particulate matter loading, and were consistent with anthropogenic inputs of metals in the estuary. Concentrations of dissolved Cu were highest in summer, whereas concentrations of Cd, Ni and Mn were significantly lower in summer than winter (P< or =0.05). The increase in temperature and biological activity during summer explained the seasonal variation. The sequence of log K(d) values (20-30 salinity) was Mn>Zn>Cu>Ni. These results give unique information concerning the contemporaneous distribution of dissolved trace metals in the Port Jackson estuary and they provide a data set against which the long-term contamination may be assessed.     

Sediments, nutrients and pesticide residues in event flow conditions in streams of the Mackay Whitsunday Region, Australia

The Mackay Whitsunday region covers 9000 km(2) in northeastern Australia. A study of diffuse pollutants during high flow events was conducted in coastal streams in this region. Sampling was conducted in the Pioneer River catchment during a high flow event in February 2002 and in Gooseponds Creek, Sandy Creek and Carmila Creek in March 2003. Concentrations of five herbicides; atrazine (1.3 microg l(-1)), diuron (8.5 microg l(-1)), 2,4-D (0.4 microg l(-1)), hexazinone (0.3 microg l(-1)) and ametryn (0.3 microg l(-1)) and high concentrations of nutrients (total nitrogen 1.14 mg l(-1), total phosphorus 0.20 mg l(-1)) and suspended sediments (620 mg l(-1)) were measured at Dumbleton Weir on the lower reaches of the Pioneer River. Drinking water guidelines for atrazine and 2,4-D were exceeded at Dumbleton Weir, low reliability trigger values for ecosystem protection for diuron were exceeded at three sites and primary industry guidelines for irrigation levels of diuron were also exceeded at Dumbleton Weir. Similar concentrations were found in the three smaller streams measured in 2003. Herbicides and fertilisers used in sugarcane cultivation were identified as the most likely major source of the herbicide residues and nutrients found.     

A micro-dilution method for detecting oxytetracycline-resistant bacteria in marine sediments from salmon and mussel aquaculture sites and an urbanized harbour in Atlantic Canada

A micro-dilution technique with changes in optical density (OD) used to measure bacterial growth over 72 h in culture media containing 0, 5, 10, 20, 40, 80 and 160 microg OTC (oxytetracycline)ml(-1) was applied to determine growth inhibition (GI) in mixed bacterial strains cultured from samples of marine sediments and salmon feed pellets. Growth of control cultures (Aeromonas salmonicida) was inhibited at all OTC concentrations. Some feed pellet samples and under-cage sediments from salmon aquaculture sites in the Bay of Fundy showed GI up to > or = 160 microg OTCml(-1). Lower values (40 to 80 microg OTC ml(-1)) occurred in subsurface (5-18 cm) sediments, > 100 m from salmon pens and adjacent to sewage outfalls in Halifax Harbour. GI values < 20 microg OTC ml(-1) in sediment from reference locations in Halifax Harbour and mussel aquaculture sites are considered to reflect natural background levels for OTC resistance.     

Copper speciation in continental inputs to the Vigo Ria: sewage discharges versus river fluxes

Continental inputs of copper via rivers and sewage into the Vigo Ria were evaluated. The main fluvial input is not contaminated and the most degraded discharges occur on the southern margin of the middle ria. Continental inputs of copper and ligands to the ria are dominated by sewage treatment plants (136 mol Cu day(-1), 124 mol L day(-1)) supported by rivers (15 mol Cu day(-1), 21 mol L day(-1)). The dissolved fraction is the main channel of discharge for rivers (66%) with particulate matter being predominant in sewage (63%). Dissolved copper is organically complexed both in rivers (99.8%) and sewage (99.9%). This minor difference may be attributed to the fact that the stability of sewage complexes is greater than those in rivers. Moreover, ligand concentrations are higher in sewage than in rivers. Thus, the natural continental inputs of copper and ligands into the ria are magnified by anthropogenic inputs (5-15 and 3-5 times higher for copper and ligands, respectively).     

Comparative concentrations of metals in marine species from French Frigate Shoals, North Pacific Ocean.

Concentrations of arsenic, cadmium, chromium, copper, lead, mercury, selenium, and zinc were measured in coral, crab, eel, fish, lobster, and sediment samples collected from French Frigate Shoals, North Pacific Ocean. The sediments contained relatively high concentrations of selenium; moderate concentrations of arsenic, cadmium, copper and lead; and low concentrations of chromium and zinc. Metal concentrations were also determined in coral and crabs collected from the island of Oahu. Notably, a crab (Grapsus tenuicrustatus) and the undulated moray eel (Gymnothorax undulatus) exhibited high levels of copper and arsenic, respectively, relative to the other species studied. The concentrations of arsenic in the eel averaged 225 microg g(-1) dry wt, which was 3-12 times higher than that in all of the other species tested. The average concentration of copper in the crab was 343 microg g(-1) dry wt, 3-86 times greater than that in the other species studied. These data indicate background and comparative levels of the metals among the studied species. Lead levels in the coral (9-10 microg g(-1) dry wt) and crab (42-57 microg g(-1) dry wt) from Tern and Disappearing Islands were 23-283-fold greater than those from Oahu (0.4 and 0.2 microg g(-1) dry wt, respectively).     

The distribution of dissolved copper in the eastern Atlantic Ocean

Dissolved copper concentrations at five stations in the eastern Atlantic between 20 and 24°N are presented. The metal is depleted in surface waters with concentrations ranging from 1.1 to 1.7 nmol/l. Marked increases in concentration were found in near-bottom waters with levels up to 10.9 nmol/l; these are attributed to the release of dissolved copper from the surface sediment.     

Effects of the herbicide diuron on the early life history stages of coral

The effects of the herbicide diuron on the early life history stages of broadcast spawning and brooding corals were examined in laboratory experiments. Fertilisation of Acropora millepora and Montipora aequituberculata oocytes were not inhibited at diuron concentrations of up to 1000 microg l(-1). Metamorphosis of symbiont-free A. millepora larvae was only significantly inhibited at 300 microg l(-1) diuron. Pocillopora damicornis larvae, which contain symbiotic dinoflagellates, were able to undergo metamorphosis after 24 h exposure to diuron at 1000 microg l(-1). Two-week old P. damicornis recruits on the other hand were as susceptible to diuron as adult colonies, with expulsion of symbiotic dinoflagellates (bleaching) evident at 10 microg l(-1) diuron after 96 h exposure. Reversible metamorphosis was observed at high diuron concentrations, with fully bleached polyps escaping from their skeletons. Pulse amplitude modulation (PAM) chlorophyll fluorescence techniques demonstrated a reduction in photosynthetic efficiency (Delta F/F(m)') in illuminated P. damicornis recruits after a 2 h exposure to 1 microg l(-1) diuron. The dark-adapted quantum yields (F(v)/F(m)) also declined, indicating chronic photoinhibition and damage to photosystem II.     

Evaluation of the mussel Perna perna as a biomonitor of polycyclic aromatic hydrocarbon (PAH) exposure and effects

The mussel Perna perna was used to monitor and assess areas suspected of oil contamination by transplanting animals from unimpacted to impacted sites and vice versa. The deployment lasted for three months during which total PAH were measured in seawater samples collected every 15 days. PAH concentrations were determined in mussel tissue monthly. The lysosomal neutral red assay and the condition index were used as biomarkers of the adverse biological effects. The PAH concentration in mussels at unimpacted sites, prior to deployment was ca. 100 microg kg(-1) but increased to 300 microg kg(-1) after three months at the contaminated site. Mussels transplanted to the uncontaminated site showed a decrease from 380 to 80 microg kg(-1). Significant changes in lysosomal stability occurred within one month of the beginning of the transposition; in contrast condition indexes were not correlated with the observed changes in PAH concentration.     

Development of a growth inhibition test with the marine and brackish water red alga Ceramium tenuicorne

The marine red macroalga Ceramium tenuicorne is cosmopolitan and naturally found in both brackish and marine waters. A growth inhibition test with this species can be carried out in salinities from 4 per thousand to 32 per thousand. The species is easily held in culture in the laboratory and the test can be performed in a completely defined medium. The robustness of the method is good with a CV of 14.6% of the controls. The EC calculations can be performed on linear regression on the length data. EC50 values of repetitive tests for zinc (20-33 microg Zn(2+)/l in 7 per thousand and 32-61 microg Zn(2+)/l in 20 per thousand) and copper (1.9-3.8 Cu(2+)/l in 7 per thousand and 7.9-13 Cu(2+)/l in 20 per thousand) show high sensitivity. This test is a good complement to any test battery with the purpose of estimating the hazard of substances to the brackish and marine environment.     

Marine risk assessment: linear alkylbenzenesulponates (LAS) in the North Sea

The fate of linear alkylbenzenesulponates (LAS) in estuaries and coastal areas of the North Sea has been characterized with simple environmental models. The predicted concentration range in the estuaries around the North Sea (0.9-9 microg LAS l(-1)) was validated by monitoring data (1-9 microg LAS l(-1)). In offshore sites of the North Sea, it is estimated--and experimentally verified for a few sites--that the LAS concentration is below analytical detection limit (i.e., 0.5 microg LAS l(-1)). The effects of LAS on marine organisms have been reviewed. For short-term acute tests, there was no significant difference (p = 0.83) between the mean LC50 values of freshwater and marine organisms (mainly pelagic species tested, 4.1 and 4.3 mg LAS l(-1), respectively). For longer-term chronic tests, it appeared that the sensitivity (mean no-observed effect concentration (NOEC) value) of marine and freshwater organisms (0.3 and 2.3 mg LAS l(-1), respectively) was significantly different pt-test = 0.007). The predicted no-effect-concentrations (PNEC) were 360 and 31 microg LAS l(-1), for freshwater and marine pelagic communities, respectively. Given that the maximum expected estuarine and marine concentrations are 3 to > 30 times lower than the PNEC, the risk of LAS to pelagic organisms in these environments is judged to be low.     

Antifouling herbicides in the coastal waters of western Japan

Residue analyses of some antifouling herbicides (Diuron, Irgarol 1051 and the latter's degradation product M1, which is also known as GS26575), were conducted in waters collected along the coast of western Japan. In total, 142 water samples were collected from fishery harbours (99 sites), marinas (27 sites), and small ports (16 sites) around the Seto Inland Sea, the Kii Peninsula, and Lake Biwa, in August 1999. A urea-based herbicide, Diuron, was positively identified for the first time in Japanese aquatic environments. Diuron was detected in 121 samples (86%) up to a highest concentration of 3.05 microg/l, and was found in 86% of samples from fishery harbours, 89% from marinas, and 75% from ports. Four freshwater samples out of 11 collected at Lake Biwa contained Diuron. Neither Irgarol 1051 nor M1 was found in the lake waters, but both were found in many coastal waters. Irgarol 1051 was found in 84 samples (60%) at a highest concentration of 0.262 microg/l. The concentrations detected were of similar magnitude to those in our previous surveys, taken in 1997 and 1998. M1 was found in 40 samples (28%) up to a highest concentration of 0.080 microg/l. The concentrations detected were generally lower than those found in our previous surveys. The detection frequency among fishery harbours, marinas, and ports was 57-70% for Irgarol 1051 and 25-30% for M1. Ninety-five per cent of the coastal waters in which M1 was detected also contained Irgarol 1051, and 93% of the samples in which Irgarol 1051 was detected also contained Diuron. These results clearly suggest that commercial ship-bottom paints containing both Diuron and Irgarol 1051 are used extensively in the survey area.     

Dissolved and particulate fluxes of copper through the Morlaix river estuary (Brittany, France): mass balance in a small estuary with strong agricultural catchment

Dissolved and particulate copper were measured over an annual cycle (12 surveys between February 1998 and January 1999) in the Morlaix Estuary (Brittany, France). These variations were investigated in both the water column and the benthic compartment in order to calculate fluxes of copper within estuary. In the water column, dissolved and particulate copper concentrations ranged from 0.6 to 19.0 nM and from 0.03 to 2.3 micromol g(-1), respectively. In the benthic compartment, copper concentrations in superficial sediment varied from 0.04 to 0.32 micromol g(-1) and from 7.6 to 80.5 nM in the pore waters. The results show that copper contents in the water column reached levels commonly observed in estuaries affected by heavy industrial activities. Agricultural activities, extensively developed on the drainage basin, may be responsible for the copper excess. Mass balance of copper indicates that the metal accumulated within the estuary with a rate ranging from 97 to 119 kg yr(-1).     

Copper accumulation by bacteria and transfer to scallop larvae

A bacterial copper-resistant strain was isolated from a hatchery-conditioned adult of the scallop Argopecten purpuratus and was identified as Vibrio sp. according to its physiological characteristics. The lowest concentration of Cu2+ required for its complete inhibition in VNSS medium was 50 microg ml(-1). The Vibrio strain was found to accumulate copper, exhibiting cellular and loosely bound copper levels of 201.14 and 493.21 microg g(-1) dry weight, respectively, after 24 h of incubation in VNSS medium supplemented with 15 microg ml(-1) of Cu2+, with cellular concentration factors of 10.17 and 14.35 after 12 and 24 h of exposure. When a scallop larvae culture was exposed to a concentration of 6.46 x 10(2) CFU ml(-1) of Cu-enriched Vibrio, they accumulated 20.42 +/- 1.12 and 30.96 +/- 1.85 microg Cu2+ g(-1) dry weight after 12 and 24 h, respectively. This study suggests that bacterial copper accumulation could be very active in marine environments increasing the occurrence of copper transfer to marine food chains.