Occurrence of volatile organic compounds (VOCs) in Liverpool Bay, Irish Sea

Surface seawater samples were collected in the Irish Sea and Liverpool Bay area from the R.V. Prince Madog during the period of 25-31 of March 2006. VOCs were purged with nitrogen, pre-concentrated on a SPME fibre and analysed immediately on a GC-MS. Target compounds quantified were halogenated (0.2-1400 ng L(-1)), BTEXs and mono-aromatics (1.5-2900 ng L(-1)), aliphatic hydrocarbons and others (0.6-15,800 ng L(-1)). Day and night sampling was performed at a single station and suggested that factors such as sunlight and tide affect the presence of many of these compounds. Sample variability was high due to the variable weather conditions at the station. Poor correlations were found between marine phytopigments and selected VOCs. Principal component analysis (PCA) analysis showed that chlorinated compounds such as 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethene, tetrachloroethene and carbon tetrachloride, predominantly from anthropogenic sources, originated from the River Mersey. Other brominated and iodinated compounds quantified were more likely to be from biogenic sources including novel marine compounds such as 2-chloropropane, 1-bromoethane and 1-chlorobutane.     

Hydrogen peroxide production rates in clean and polluted coastal marine waters of the Mediterranean, Red and Baltic Seas

The main aim of this study was to assess the hydrogen peroxide (HP) production rates (HPPR) related to anthropogenic pollution in coastal waters by laboratory and field experiments. HPPR's were assessed by simultaneous measurements of HP concentrations, cumulative solar UV irradiation and dissolved organic matter (DOM) fluorescence in the seawater samples at clean and polluted sites in the Mediterranean, Red and the Baltic Seas. The natural HP concentrations at all sites (8–100 nM) fall within the normal range recorded elsewhere, and follows a diurnal pattern. The polluted stations in the Mediterranean and Baltic Seas showed higher HPPR (3.2–16.6 nM m² W⁻¹ h⁻¹) than the clean stations, while in the Red Sea no significant differences were found because the station that was considered a priori polluted was actually rather clean (2–3 nM m² W⁻¹ h⁻¹). Laboratory experiments demonstrated that HPPR was positively linearly correlated to DOM fluorescence, however, this relationship was not found in the natural seawater samples examined in the field. The lack of relationship between HPPR and DOM in the field was attributed to enzymatic breakdown of HP as observed in dark decay experiments. HP dark decay rates were highest in polluted stations, probably due to larger bacterioplankton populations in these samples. Moreover, the HP dark decay rates were much lower in filtered than in non-filtered samples. Sun incubation of filtered (0.2 μm) seawater samples were performed to assess whether elimination of particles would yield higher HPPRs than in non-filtered samples. In the Baltic Sea (low UV irradiation) HPPR was higher in the filtered samples, while at sites with relatively high UV irradiation (Mediterranean and Red Seas), filtration of seawater did not stimulate HPPRs, probably due to UV-damage to planktonic microorganisms.     

Regional distribution of halogenated organophosphate flame retardants in seawater samples from three coastal cities in China

Thirteen samples of seawater were collected from Yellow Sea and East China Sea near Qingdao, Lianyungang, and Xiamen, China. They were analyzed for halogenated organophosphorus flame retardants (OPFRs). The compounds selected for detection were Tris(2-chloroethyl) phosphate (TCEP), Tris(2-chloroisopropyl) phosphate (TCPP), Tris (1,3-dichloro-2-propyl) phosphate (TDCPP), and Tris(2,3-dibromopropyl) phosphate (TDBPP). The total concentrations ranged from 91.87 to 1392 ng/L and the mean concentrations of these four chemicals were 134.44, 84.12, 109.28, and 96.70 ng/L, respectively. TCEP exhibited the highest concentrations, although concentrations of TCPP and TDCPP were also fairly high in Lianyungang and Xiamen. Generally, Lianyungang was the most heavily polluted district, with very high concentrations of TCEP at LYG-2 (550.54 ng/L) and LYG-4 (617.92 ng/L). The main sources of halogenated OPFRs were municipal and industrial effluents of wastewater treatment plants in the nearby economic and industrial zones.     

Bioaccumulation factors of chlorinated hydrocarbons between mussels and seawater

The bioaccumulation of PCB and DDT compounds by mussels, Mytilus spp., from ambient seawater was determined by measuring concentrations of these chlorinated hydrocarbons in both mussels and seawater at four sites on the Mediterranean coast of France and two sites in California. Bioaccumulation factors were found to vary over an order of magnitude. Ratios of the concentrations of PCB in mussels, consisting predominantly of pentachloro-and hexachlorobiphenyls, to concentrations in ambient seawater ranged between 69 000 and 690 000; the corresponding ratios of concentrations of p,p′-DDE or p,p′-DDT ranged from 40 000 to 690 000. Although mussels appear to be appropriate and convenient indicator organisms of local chlorinated hydrocarbon contamination levels, the factors contributing to this variance must be determined before mussels are widely used in global monitoring programmes.     

The distribution of short-chain halogenated aliphatic hydrocarbons in some marine organisms

A number of halogenated aliphatic hydrocarbons have been determined in the various organs of three species of molluscs and five species of fish. In general, the compounds were only slightly enriched (2–25 times) on a dry weight basis relative to their seawater concentrations. The usual order of enrichment was found to be brain > gill > liver > muscle. Methyl iodide was found to be the compound most strongly concentrated.     

A survey to determine levels of chlorinated pesticides and PCBs in mussels and seawater from the Mid-Black Sea Coast of Turkey

A mussel and seawater monitoring survey was conducted at six sampling points between Yalikoy (Ordu) and Sinop in 1999-2000 along the Mid-Black Sea Coast of Turkey in order to assess concentrations of organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs). Chlorinated pesticides and PCBs were measured in the mussel Mytilus Galloprovincialis and in seawater. In the mussel samples, the most common pollutants in terms of average concentration per g of wet weight (ww), were DDT (max. 1800 pg/gww, min. 240 pg/gww) and its metabolites DDD (max. 5400 pg/gww, min. 240 pg/gww) and DDE (max. 2800 pg/gww, min. 70 pg/gww). Also, dieldrin, heptachlor and HCB were notable contaminants in the mussel samples. PCBs were determined in none of the biota or seawater samples. The concentrations of the OCs and PCBs in mussels were higher in coastal areas receiving river discharges and close to the largest city of the region, Samsun (especially in sampling points in the harbour area). The well-known long persistence of DDTs and other chlorinated compounds was confirmed by residues of these pollutants measured in mussels. On the other hand, even though the usage of such kind of persistent compounds in Turkey was banned, there may still be illegal usage and it is not certain whether the application of these compounds did end in the region.     

The Sensitivity of Four Monitoring Well Sampling Systems to Low Concentrations of Three Volatile Organics

Four state-of-the-art ground water sampling systems were analyzed to determine their reliability in providing representative samples of the volatile chlorinated hydrocarbons trichloroethylene (TCE), perchloroethylene (PCE), and 1,1,1-trichloroethane (TCA) from a simulated monitoring well. The sampling systems studied represent four commonly used devices, including a stainless steel and Teflon® piston pump, a Teflon bailer, a Teflon bladder pump, and a PVC air-lift pump.
Controlled laboratory sampling experiments were conducted in a tank and well test chamber designed to approximate field conditions. A well purging and sampling procedure was used in the test apparatus to determine the accuracy and precision of each device for detecting low concentrations of the compounds in ground water. The compounds selected are some of the most ubiquitous hazardous contaminants found in shallow aquifers near hazardous waste sites throughout the United States.
No significant statistical difference was found among the four sampling systems in detecting the compounds.     

The effect of thermal pollution on benthic foraminiferal assemblages in the Mediterranean shoreface adjacent to Hadera power plant (Israel)

The thermal pollution patch of Hadera power plant was used as a natural laboratory to evaluate the potential long-term effects of rise in Eastern Mediterranean SST on living benthic foraminifera. Their sensitivity to environmental changes makes foraminifera ideal for this study. Ten monthly sampling campaigns were performed in four stations located along a temperature gradient up to 10 °C from the discharge site of heated seawater to a control station. The SST along this transect varied between 25/18 °C in winter and 36/31 °C in summer. A significant negative correlation was found between SST in all stations and benthic foraminiferal abundance, species richness and diversity. The total foraminiferal abundance and species richness was particularly low at the thermally polluted stations especially during summer when SST exceeded 30 °C, but also throughout the entire year. This indicates that thermal pollution has a detrimental effect on benthic foraminifera, irrelevant to the natural seasonal changes in SST.     

Trihalomethane im Trinkwasser

In three water works investigations were performed on the formation of halogenated hydrocarbons resulting from chlorination and the results are given. There were exclusively detected halogenated methane compounds with concentrations below 25 μg/1 and therefore agreeing with values already reported. Trichloronitromethane was detected, too; its concentration correlates with the nitrite content of water.     

Setting new thermal standards for transitional and coastal (TraC) waters

The construction of a new generation of coastal power stations in the UK and other western European countries has highlighted the absence of robust standards for thermal discharges to transitional and coastal waters. The proposed discharge volumes are greater than hitherto, yet there has been little independent critical examination of their potential impact, whilst much of the existing guidance has been adapted from freshwater practice. This review considers the available knowledge on the tolerance and behaviour of fish and other marine biota to heated effluents. Appropriate ways are suggested of grouping fish species to reflect their sensitivity to thermal effects. The plethora of existing standards are considered and their validity assessed in a framework of predicted seawater temperature rise. Those species or groups of organisms most likely to be affected are identified and finally specific recommendations for thermal standards consistent with long term sustainability are proposed.     

Interactions of Chlorine with Natural Organic Matter and Formation of Intermediates: Evidence by Differential Spectroscopy

This communication describes the use of differential absorbance spectroscopy to explore the intermediates formed during halogenation of natural organic matter (NOM). The differential spectra of chlorinated NOM comprise two contributions. The primary component is negative and has a peak near 270 nm. The shape of this band is independent of chlorine dose, and its intensity increases monotonically with Cl₂ dose. The second component is positive, with a well‐defined peak near 280 nm and another, broader band in the 340...380 nm range. The second component is noticeable at low chlorine concentrations but disappears with increasing Cl₂ dose. We attribute this component to aromatic chlorinated intermediates formed prior to the release of identifiable smaller species such as haloacetic acids. We believe that this component of the differential spectra can be used to probe the identity, formation and breakdown of the halogenated intermediates.     

Review of Abiotic Degradation of Chlorinated Solvents by Reactive Iron Minerals in Aquifers

Abiotic degradation of chlorinated solvents by reactive iron minerals such as iron sulfides, magnetite, green rust, and other Fe(II)‐containing minerals has been observed in both laboratory and field studies. These reactive iron minerals form under iron‐ and sulfate‐reducing conditions which are commonly found in permeable reactive barriers (PRBs), enhanced reductive dechlorination (ERD) treatment locations, landfills, and aquifers that are chemically reducing. The objective of this review is to synthesize current understanding of abiotic degradation of chlorinated solvents by reactive iron minerals, with special focus on how abiotic processes relate to groundwater remediation. Degradation of chlorinated solvents by reactive minerals can proceed through reductive elimination, hydrogenolysis, dehydrohalogenation, and hydrolysis reactions. Degradation products of abiotic reactions depend on degradation pathways and parent compounds. Some degradation products (e.g., acetylene) have the potential to serve as a signature product for demonstrating abiotic reactions. Laboratory and field studies show that various minerals have a range of reactivity toward chlorinated solvents. A general trend of mineral reactivity for degradation of chlorinated solvents can be approximated as follows: disordered FeS > FeS > Fe(0) > FeS₂ > sorbed Fe²⁺ > green rust = magnetite > biotite = vermiculite. Reaction kinetics are also influenced by factors such as pH, natural organic matter (NOM), coexisting metal ions, and sulfide concentration in the system. In practice, abiotic reactions can be engineered to stimulate reactive mineral formation for groundwater remediation. Under appropriate site geochemical conditions, abiotic reactions can occur naturally, and can be incorporated into remedial strategies such as monitored natural attenuation.     

Geochemical survey of Levante Bay,Vulcano Island (Italy), a natural laboratory for the study of ocean acidification

Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO₂ per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO₂ leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO₂ levels. This shoreline lacks toxic compounds (such as H₂S) and has a gradient in carbonate saturation states.     

Laboratory investigation of the effects of mineral size and concentration on the formation of oil-mineral aggregates

Controlled laboratory studies of the formation of oil-mineral aggregates (OMA) in seawater demonstrate that sediment concentration and sediment size are key variables for determining the quantity of oil droplets stabilised by OMA formation. Experiments with a single sediment size and a range of sediment concentrations show that as sediment concentration increases, the quantity of oil trapped in OMA increases abruptly. In experiments with a single sediment concentration and a range of sediment sizes, the quantity of oil trapped in OMA decreases as sediment size increases. These results provide direct support to the hypothesis that there is a critical sediment concentration for OMA formation. Below this concentration, stabilisation of oil droplets by OMA decreases rapidly, while above this concentration, stabilisation is extensive. The results also support simple geometric models of OMA formation that predict that the critical sediment mass concentration increases linearly with sediment particle diameter. These results will help to place quantitative constraint on predictions of where and when OMA formation will be a factor in the natural dispersal of oil accidentally spilled into the ocean.     

Changes in hydraulic conductivity of laboratory sand-clay mixtures caused by a seawater-freshwater interface

The influence of small amounts of clay minerals on the hydraulic conductivity of sandy aquifer was investigated by laboratory experiments. Admixture of up to 1.5% by weight of clay minerals to sand did not cause any measurable decrease of hydraulic conductivity for seawater. Increasing the clay fraction from 1.5% to 10% decreased hydraulic conductivity by one order of magnitude. Montmorillonite caused the strongest decrease; the effect of kaolinite and illite was only half as large. When seawater was flushed by freshwater, hydraulic conductivity of the montmorillonite-sand mixture decreased drastically. However, flushing with freshwater did not measurably affect the hydraulic conductivity of an illite-sand or kaolinite-sand mixture. The explanation for this behaviour is the capability of various types of clay to adsorb different quantities of water between their platelets which induces a gel-droplet formation process. This is governed by the chemical composition and the ionic strength of the solution.     

Seasonal and spatial distribution of nonylphenol and IBP in Saemangeum Bay, Korea

In order to investigate spatial and temporal distribution of organic pollutants in the Saemangeum Bay, organophosphorus pesticides (10), alkylphenols (8), chlorophenols (2), bisphenol A were analyzed from the surface seawater taken in 2002–2003. Most of the analytes were not detected in all stations except nonylphenol and S-benzyl-O,O-di-isopropyl phosphorothioate (IBP). Concentrations of nonylphenol and IBP ranged from ND to 298 ng/l and from ND to 1840 ng/l, respectively. The high levels of nonylphenol and IBP were found in the estuary areas of Mangyeong and Dongjin River. The levels of nonylphenol and IBP in surface seawater varied through seasons and the high levels of nonylphenol and IBP were in summer season (August). Based on real time monitoring of IBP and on correlation between concentrations of target compounds and contents of salinity in seawater, physical mixing and diffusion of seawater were found to be the major factors that affect the spatial distribution of IBP and nonylphenol in the Saemangeum Bay environment.     

Der Einfluss von gereinigtem Abwasser auf das Phytoplankton in Seen

The effect of domestic sewage effluents after a) mechanical, b) mechanical-biological and c) mechanical-biological-chemical treatment on algal cultures and on natural lake phytoplankton was studied by means of laboratory assays and in situ experiments. The concentrations of phosphorus and nitrogen are almost exclusively responsible for any algal growth. Other constituents which may be present in sewage effluents (e.g. residual amounts of iron originating from the tertiary treatment) do not stimulate substantially the growth of algae.     

Status of butyltin pollution along the coasts of western Japan in 2001, 11 years after partial restrictions on the usage of tributyltin

Restrictions on the use of tributyltin (TBT) in aquaculture and on boats in coastal regions, except for ocean-going vessels, have been in place in Japan since 1990 due to the strong toxic effects of TBT on marine organisms. However, TBT pollution along the Japanese coasts has been reported after this legislation was enacted. In order to elucidate the present status of contamination by butyltin (BT) compounds, we measured the levels of BTs [monobutyltin (MBT), dibutyltin (DBT) and TBT] in seawater and Caprella spp. samples obtained from the western part of Seto Inland Sea, Uwa Sea and Uranouchi Bay in western Japan during March to September, 2001. Butyltins were detected in more than 90% of the seawater samples (n = 59), with average concentrations of 8.2 ± 9.2 (SD) ng MBT L⁻¹, 3.3 ± 3.0 ng DBT L⁻¹ and 9.0 ± 7.0 ng TBT L⁻¹. Among 41 stations situated on coastal lines, a sufficient number of Caprella organisms for chemical analysis could be collected from only 16 stations. The butyltin concentrations in seawater and Caprella samples from Uwa Sea and Uranouchi Bay, in which the dominant industry in both waters is aquaculture, showed significantly higher than or no significant differences from those samples from the western part of Seto Inland Sea, a major heavy-industry area in Japan. As the TBT concentration in seawater increased, the number of Caprella organisms collected decreased. The mean TBT concentration among the seawater samples was above the estimated lowest observable effect concentration (LOEC) that reduces the survival rate of Caprella danilevskii. Thus, the present study indicates that TBT is still a potential ecological hazard to the survival of marine invertebrates inhabiting coasts along western Japan, even 11 years after the partial ban on TBT usage was implemented.     

The effects of biological fouling control at coastal and estuarine power stations

The use of low levels of oxidants as antifouling agents in coastal and estuarine power station cooling water circuits can give rise to concerns over the likely production of chlorination byproducts (CBPs) including organohalogens, of largely cryptic identity, loading and impact. In order to review the current understanding of the degree of impact involved this paper describes a recent collaborative programme of work on CBPs within the wider context of a number of allied studies on power station cooling water entrainment and discharge effects. Bromoform was the single most important CBP found in coastal power station effluents. Although bromoform was found to accumulate in the liver of the sea bass Dicentrarchus labrax (L.) continuously exposed to a chlorinated effluent stream, no otherwise untoward impact on continuously exposed individuals was discerned. Populations of the common blue mussel Mytilus edulis L., likewise exposed, exhibited two responses: a high degree of genoplasticity and the evolution of stress proteins--although both may have been due to thermal rather than toxic stress. Experiments on plankton that simulated the conditions of entrainment within cooling water systems isolated the influence of oxidant usage, with mortality varying between taxa and life stage. The results suggest a very limited impact of oxidant use and the associated CBPs on receiving waters both in terms of plume toxicity or any more widespread ecotoxicological influence. Instead, it is in combination with applied temperature (DeltaT), pressure and the other stressors involved in entrainment within the power station cooling water circuits themselves that an impact is most marked.     

Biodegradation of Creosote Compounds: Comparison of Experiments at Different Scales

This paper compares the results of biodegradation experiments with creosote compounds performed at different scales. The experiments include field observations, field experiments, large-scale intact laboratory column experiments, model fracture experiments, and batch experiments. Most of the experiments were conducted with till or ground water from the field site at Ringe on the island of Funen. Although the experiments were conducted on different scales, they revealed that some phenomena—e.g., an extensive biodegradation potential of several of the creosote compounds, the inhibitory influence of the pyrroles on the biodegradation of benzene, and the biodegradation of benzothiophene occurs only in the presence of a primary substrate. The experiments show that some biodegradation processes of organic compounds may be common to different microorganisms.