High frequency monitoring of the coastal marine environment using the MAREL buoy

The MAREL Iroise data buoy provides physico-chemical measurements acquired in surface marine water in continuous and autonomous mode. The water is pumped 1.5 m from below the surface through a sampling pipe and flows through the measuring cell located in the floating structure. Technological innovations implemented inside the measuring cell atop the buoy allow a continuous cleaning of the sensor, while injection of chloride ions into the circuit prevents biological fouling. Specific sensors for temperature, salinity, oxygen and fluorescence investigated in this paper have been evaluated to guarantee measurement precision over a 3 month period. A bi-directional link under Internet TCP-IP protocols is used for data, alarms and remote-control transmissions with the land-based data centre. Herein, we present a 29 month record for 4 parameters measured using a MAREL buoy moored in a coastal environment (Iroise Sea, Brest, France). The accuracy of the data provided by the buoy is assessed by comparison with measurements of sea water weekly sampled at the same site as part of SOMLIT (Service d'Observation du Milieu LIToral), the French network for monitoring of the coastal environment. Some particular events (impact of intensive fresh water discharges, dynamics of a fast phytoplankton bloom) are also presented, demonstrating the worth of monitoring a highly variable environment with a high frequency continuous reliable system.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

Distribution of Iron, Manganese, Zinc and Atrazine in Groundwater in Parts of Palar and Cheyyar River Basins, South India

A study was carried out in a part of Palar and Cheyyar river basin to evaluate the current status of iron, manganese, zinc and atrazine concentrations, their origin and distribution in groundwater. Groundwater samples were collected during post-monsoon (March 1998 and February 1999) and pre-monsoon (June 1999) periods from 41 sampling wells distributed throughout the study area. The groundwater samples were analyzed for trace metals using AAS and atrazine using HPLC. The concentration of the trace elements in groundwater is predominant during pre-monsoon period. Distribution pattern indicates that the concentration of these elements increases from west to northeast and towards Palar river. Lower concentrations in the central part may be due to recharge of fresh water from the lakes located here. During most of the months, as there is no flow in Palar river, the concentrations of trace elements in groundwater are high. Drinking water standards indicate that Mn and Zn cross the permissible limit recommended by EPA during the pre-monsoon period. A comparison of groundwater data with trace element chemistry of rock samples shows the abundance of trace elements both in the rock and water in the order of Fe > Mn > Zn and Fe > Zn > Mn. This indicates that iron in groundwater is derived from lithogenic origin. Further, Fe, Mn and Zn have good correlation in rock samples, while it is reverse in the case of water samples, indicating the non-lithogenic origin of Mn and Zn. Atrazine (a herbicide) was not detected in any of the groundwater samples in the study area, perhaps due to low-application rate and adsorption in the soil materials.     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

Exposure and inhalation risk assessment in an aluminium cast-house

To date the exposure, absorption and respiratory health effects of cast-house workers have not been described since most studies performed in the aluminium industry are focused on exposure and health effects of potroom personnel. In the present study, we assessed the external exposure and the absorbed dose of metals in personnel from the aluminium cast house. This was combined with an evaluation of respiratory complaints and the lung function of the personnel. 30 workers from an aluminium casting plant participated and 17 individuals of the packaging and distribution departments were selected as controls. The exposure was assessed by the quantification of total inhalable fume with metal fraction and by the determination of urinary aluminium, chromium, beryllium, manganese and lead concentration. Carbon monoxide (CO), carbon dioxide (CO2), aldehydes and polyaromatic hydrocarbons and man-made mineral fibres concentration were assessed as well. In order to evaluate their respiratory status each participant filled out a questionnaire and their lung function was tested by forced spirometry. Total inhalable fume exposure was maximum 4.37 mg m(-3). Exposure to the combustion gases, man-made mineral fibres and metal fume was well below the exposure limits. Beryllium could not be detected in the urine. The values of aluminium, manganese and lead in the urine were all under the respective reference value. One individual had a urinary chromium excretion above the ACGIH defined biological exposure index (BEI) of 30 microg g(-1) creatinine. There was no significant difference in any of the categories of the respiratory questionnaire and in the results of the spirometry between cast house personnel and referents (Chi-square, all p > 0.05). Exposure in cast houses seem to be acceptable under these conditions. However, peak exposure to fumes cannot be excluded and the potential risk of chromium and beryllium exposure due to the recycling of aluminium requires further attention.     

Interlaboratory evaluation of endotoxin analyses in agricultural dusts--comparison of LAL assay and mass spectrometry

Endotoxin exposure is associated with wheeze and asthma morbidity, while early life exposure may reduce risk of allergy and asthma. Unfortunately, it is difficult to compare endotoxin results from different laboratories and environments. We undertook this study to determine if lipopolysaccharide (LPS) extraction efficiency could account for differences among laboratories. We generated and collected aerosols from chicken and swine barns, and corn processing. We randomly allocated side-by-side filter samples to five laboratories for Limulus assay of endotoxin. Lyophilized aliquots of filter extracts were analyzed for 3-hydroxy fatty acids (3-OHFAs) as a marker of LPS using gas chromatography-mass spectrometry. There were significant differences in endotoxin assay and GC-MS (LPS) results between laboratories for all dust types (p < 0.01). Patterns of differences between labs varied by dust type. Relationships between assay and GC/MS results also depended on dust type. The percentages of individual 3-OHFA chain lengths varied across labs (p < 0.0001) suggesting that each lab recovered a different fraction of the LPS available. The presence of large amounts of particle associated LPS and absence of a freezing thawing cycle were associated with lower correlations between LPS and bioactivity, consistent with an absence of Limulus response to cell-bound endotoxin. These data suggest that extraction methods affect endotoxin measurements. The LAL methods may be most suitable when comparing exposures within similar environments; GC-MS offers additional information helpful in optimizing sample treatment and extraction. GC-MS may be of use when comparing across heterogeneous environments and should be considered for inclusion in future studies of human health outcomes.     

Organic contaminants in the Firth of Clyde following the cessation of sewage sludge dumping

To assess contaminant concentrations in the Firth of Clyde in relation to the former sewage sludge dump site at Garroch Head, and investigate any temporal changes, fish have been sampled annually since 1992 and sediment since 1999. In addition, a further four locations in the Clyde (Holy Loch, Hunterston, Skelmorlie and Irvine Bay) have been sampled for fish and sediment since 1999. Chlorobiphenyls (CBs) were measured in fish samples and polycyclic aromatic hydrocarbons (PAHs) and CBs in sediment. Since sampling was initiated the concentration for the summation operatorICES7 CBs in fish liver has been consistently >500 microg kg(-1) lipid weight at Garroch Head and the other Clyde sites and lower at the reference sites (Pladda, Colonsay, Broad Bay). Although the lowest CB concentrations of the eleven year period in plaice liver from Garroch Head were found in 2002, CB concentrations were found not to have decreased significantly since sewage sludge dumping ceased in 1998. However, a change in CB profile was observed with fish liver collected between 1992 and 1998 from Garroch Head showing a lower proportion of the less chlorinated CBs compared to the 1999-2002 liver samples. Highest CB and PAH concentrations in sediment were found at Garroch Head and Holy Loch with concentrations at these sites being significantly higher than at all other sites.     

Biomonitoring heavy metals in estuaries: a field comparison of two brown algae species inhabiting upper estuarine reaches

Biomonitoring dissolved heavy metals within estuaries,particularly at their upper reaches, frequently has to relyon several biomonitors; rarely a single species thrives allalong the salinity gradient. To properly do so, it must beestablished whether those biomonitors actually accumulateheavy metals alike. In this study, two brown seaweeds fromthe upper section of three NW Spain estuaries – the widely-known Fucus vesiculosus and the estuarine Fucusceranoides – were compared as metal biomonitors. Bothspecies were collected at five locations where they eithercoexist or live close to each other and their heavy metalcontent (Cu, Cr, Mn, Zn, Fe, Al) was measured. Analyseswere appropriately replicated for each species x locationcombination to allow a statistically reliable detection ofdifferences in bioaccumulation, with particular emphasis onthe magnitude of interspecific differences. The lack of significant differences for Cu, Mn, and Zncontents in F. ceranoides and F. vesiculosussupports the feasibility of their joint use to monitorthese metals along the estuaries. Conversely, F.ceranoides concentrated significantly higher levels of Cr,Fe, and Al than F. vesiculosus and hence combiningdata for both fucoids to monitor these elements seemsimpractical. The correlation of species differencestogether with a similar Al:Fe ratio in both weed tissue andsediment suggest that Cr, Fe, and Al tissue-burdens mightbe considerably biased by sediment retained on the surfaceof the weed. Parallel analyses of Al and/or Fe in seaweedsand sediments could serve to keep track of thisinterference and may help to combine data from both fucoidsfor monitoring elements like Cr.     

Large-scale mercury variations in Lake Vänern (Sweden) 1974-98

Lake V?nern, the largest lake in Sweden, has been seriously contaminated with mercury during the 20th century. In the 1970's and 80's the direct load, mainly from a chlor-alkali industry in the area, of mercury was drastically reduced as a response to new legislation, from three to five tons down to between five and ten kg yr(-1). Large amounts of the disposed pollutant have accumulated in the sediments. The question posed in this work is now, is the effect of the drastic load reduction after more than two decades visible in the sediments? The question is relevant as large areas still are blacklisted for fishing, but also as a follow-up of a major remedy action. The lake also serves as a freshwater reservoir for even Sweden's second largest city. This work synthesises and compares data of mercury in the sediments from three major field programs, in 1974, 1984 and 1998. The interest is focused on both spatial heterogeneity and temporal trends. In 1974, the surface concentrations are significantly higher than in subsequent surveys. Significant differences are also found between 1984 and 1998. Significant spatial differences within the lake are found for respective year. The most contaminated area is located in the north, close to the major point source (a former chlor-alkali industry). This is also the area with the largest improvement, as a direct response to the reduction in load. Further from the outlet, the recovery is more affected by burial and transport processes out into the deeper basins.     

Effect of an industrial discharge on water quality and periphyton structure in a pampeam stream

Seasonal sampling was carried out at four sites on a pampeanstream that receives industrial effluent from two textile factories. To evaluate water quality, several physical and chemical parameters were examined and the periphyton growing oncattail (Typha latifolia L.) were analyzed.Water quality and periphyton structure differed significantlybetween sites upstream and downstream of the discharge. Differences in temperature and also in concentrations of phosphate, dissolved oxygen, and phaeopigment were detected. At the same time, changes in the dominant algae groups wereobserved. Downstream of the industrial discharge, the numberof Bacillariophyta decreased, while species of Cianophyta andEuglenophyta were more abundant. This abundance correlated withincreased phosphate and organic matter content and decreased oxygen concentration. Although this study did not detect a reduction in the number of species, similarity between stands decreased downstream of the industrial discharge. Changes incommunity structure were readily detected in this situation because the communities of the polluted and unpolluted zones were qualitatively different. Periphyton growing naturally on Typha latifolia is a useful indicator of the impact of waste waters on the biota and can also be used to evaluate water body recovery.