Bioavailability and toxicity of chemicals in inland waters : the importance of prevailing water chemistry and implications for risk assessment

Physicochemical characterization of freshwater samples from Finland, Sweden, the Netherlands, and Spain revealed that water hardness and pH decreased and the quantity and quality of humic substances changed considerably in this geographical series from south to north. Since the ambient water chemistry may affect the availability of chemicals, the total aqueous concentration of a chemical may be insufficient to predict the bioconcentration, subsequent biological response, and thus risk. In addition, organisms could be affected directly by water quality characteristics. In this context the main objective of this thesis was to investigate the bioavailability of selected ecotoxicologically relevant chemicals (cadmium, benzo(a)pyrene, and pyrene) in various European surface waters and to show the importance of certain water chemistry characteristics in interpreting the bioavailability and toxicity results. The bioavailability of cadmium to Daphnia magna was examined in very soft humic lake water. Humic substances as natural ligands decreased the free and bioavailable proportion of cadmium in soft lake water. As a consequence the uptake rate and the acute toxicity decreased compared with the humic-free reference. When the hardness of humic lake water was artificially elevated, the acute toxicity of cadmium decreased, although the proportion of free cadmium increased. The decreased bioavailability of cadmium in hard water was a result of effective competition for uptake by the hardness cations, especially calcium ions. The protective role of humic substances and water hardness against cadmium toxicity was also observed in Lumbriculus variegatus, although D. magna was more sensitive to cadmium. The bioavailability of two polycyclic aromatic hydrocarbons (PAHs), pyrene and benzo(a)pyrene, was studied in European surface waters of varying water chemistry. Humic substances acted as complexing ligands with both PAHs, but the bioavailability of the more lipophilic benzo(a)pyrene to D. magna was affected more by humic substances than that of pyrene. In addition, not only the quantity of humic substances, but also their quality affected the bioavailability of benzo(a)pyrene. Nevertheless, the humic substances played a protective role in the photo-enhanced toxicity of pyrene under UV-B radiation. Water hardness had no effect on pyrene toxicity. Results indicate that the typical physicochemical characteristics of boreal freshwaters should be considered carefully in local and regional risk assessment of chemicals concerning the Fennoscandian region.

Ecological condition of coastal ocean waters along the U.S. Western Continental Shelf: 2003

Executive Summary: The western National Coastal Assessment (NCA-West) program of EPA, in conjunction with the NOAA National Ocean Service (NOS), conducted an assessment of the status of ecological condition of soft sediment habitats and overlying waters along the western U.S. continental shelf, between the target depths of 30 and 120 m, during June 2003. NCA-West and NOAA/NOS partnered with the West Coast states (Washington (WA), Oregon (OR), and California (CA)), and the Southern California Coastal Water Research Project (SCCWRP) Bight ’03 program to conduct the survey. A total of 257 stations were sampled from Cape Flattery, WA to the Mexican border using standard methods and indicators applied in previous coastal NCA projects. A key study feature was the incorporation of a stratified-random sampling design with stations stratified by state and National Marine Sanctuary (NMS) status. Each of the three states was represented by at least 50 random stations. There also were a total of 84 random stations located within NOAA’s five NMSs along the West Coast including the Olympic Coast NMS (OCNMS), Cordell Bank NMS (CBNMS), Gulf of Farallones NMS (GFNMS), Monterey Bay NMS (MBNMS), and Channel Islands NMS (CINMS). Collection of flatfish via hook-and-line for fish-tissue contaminant analysis was successful at 50 EMAP/NCA-West stations. Through a collaboration developed with the FRAM Division of the Northwest Fisheries Science Center, fish from an additional 63 stations in the same region and depth range were also analyzed for fish-tissue contaminants. Bottom depth throughout the region ranged from 28 m to 125 m for most stations. Two slightly deeper stations from the Southern California Bight (SCB) (131, 134 m) were included in the data set. About 44% of the survey area had sediments composed of sands (< 20% silt-clay), about 47% was composed of intermediate muddy sands (20-80% silt-clay), and about 9% was composed of muds (> 80% silt-clay). The majority of the survey area (97%) had relatively low percent total organic carbon (TOC) levels of < 2%, while a small portion (< 1%) had high TOC levels (> 5%), in a range potentially harmful to benthic fauna. Salinity of surface waters for 92% of the survey area were > 31 psu, with most stations < 31 psu associated with the Columbia River plume. Bottom salinities ranged only between 31.6 and 34.4 psu. There was virtually no difference in mean bottom salinities among states or between NMS and non-NMS stations. Temperatures of surface water (range 8.5 -19.9 °C) and bottom water (range 5.8 -14.7 °C) averaged several degrees higher in CA in comparison to WA and OR. The Δσt index of watercolumn stratification indicated that about 31% of the survey area had strong vertical stratification of the water column. The index was greatest for waters off WA and lowest for CA waters. Only about 2.6 % of the survey area had surface dissolved oxygen (DO) concentrations ≤ 4.8 mg/L, and there were no values below the lower threshold (2.3 mg/L) considered harmful to the survival and growth of marine animals. Surface DO concentrations were higher in WA and OR waters than in CA, and higher in the OC NMS than in the CA sanctuaries. An estimated 94.3% of the area had bottom-water DO concentrations ≤ 4.8 mg/L and 6.6% had concentrations ≤ 2.3 mg/L. The high prevalence of DO from 2.3 to 4.8 mg/L (85% of survey area) is believed to be associated with the upwelling of naturally low DO water across the West Coast shelf. Mean TSS and transmissivity in surface waters (excluding OR due to sample problems) were slightly higher and lower, respectively, for stations in WA than for those in CA. There was little difference in mean TSS or transmissivity between NMS and non-NMS locations. Mean transmissivity in bottom waters, though higher in comparison to surface waters, showed little difference among geographic regions or between NMS and non-NMS locations. Concentrations of nitrate + nitrite, ammonium, total dissolved inorganic nitrogen (DIN) and orthophosphate (P) in surface waters tended to be highest in CA compared to WA and OR, and higher in the CA NMS stations compared to CA non-sanctuary stations. Measurements of silicate in surface waters were limited to WA and CA (exclusive of the SCB) and showed that concentrations were similar between the two states and approximately twice as high in CA sanctuaries compared to OCNMS or nonsanctuary locations in either state. The elevated nutrient concentrations observed at CA NMS stations are consistent with the presence of strong upwelling at these sites at the time of sampling. Approximately 93% of the area had DIN/P values ≤ 16, indicative of nitrogen limitation. Mean DIN/P ratios were similar among the three states, although the mean for the OCNMS was less than half that of the CA sanctuaries or nonsanctuary locations. Concentrations of chlorophyll a in surface waters ranged from 0 to 28 μg L-1, with 50% of the area having values < 3.9 μg L-1 and 10% having values > 14.5 μg L-1. The mean concentration of chlorophyll a for CA was less than half that of WA and OR locations, and concentrations were lowest in non-sanctuary sites in CA and highest at the OCNMS. Shelf sediments throughout the survey area were relatively uncontaminated with the exception of a group of stations within the SCB. Overall, about 99% of the total survey area was rated in good condition (<5 chemicals measured above corresponding effect range low (ERL) concentrations). Only the pesticides 4,4′-DDE and total DDT exceeded corresponding effect range-median (ERM) values, all at stations in CA near Los Angeles. Ten other contaminants including seven metals (As, Cd, Cr, Cu, Hg, Ag, Zn), 2-methylnaphthalene, low molecular weight PAHs, and total PCBs exceeded corresponding ERLs. The most prevalent in terms of area were chromium (31%), arsenic (8%), 2-methylnaphthalene (6%), cadmium (5%), and mercury (4%). The chromium contamination may be related to natural background sources common to the region. The 2-methylnaphthalene exceedances were conspicuously grouped around the CINMS. The mercury exceedances were all at non-sanctuary sites in CA, particularly in the Los Angeles area. Concentrations of cadmium in fish tissues exceeded the lower end of EPA’s non-cancer, human-health-risk range at nine of 50 EMAP/NCA-West and nine of 60 FRAM groundfish-survey stations, including a total of seven NMS stations in CA and two in the OCNMS. The human-health guidelines for all other contaminants were only exceeded for total PCBs at one station located in WA near the mouth of the Columbia River. Benthic species richness was relatively high in these offshore assemblages, ranging from 19 to 190 taxa per 0.1-m2 grab and averaging 79 taxa/grab. The high species richness was reflected over large areas of the shelf and was nearly three times greater than levels observed in estuarine samples along the West Coast (e.g NCA-West estuarine mean of 26 taxa/grab). Mean species richness was highest off CA (94 taxa/grab) and lower in OR and WA (55 and 56 taxa/grab, respectively). Mean species richness was very similar between sanctuary vs. non-sanctuary stations for both the CA and OR/WA regions. Mean diversity index H′ was highest in CA (5.36) and lowest in WA (4.27). There were no major differences in mean H′ between sanctuary vs. nonsanctuary stations for both the CA and OR/WA regions. A total of 1,482 taxa (1,108 to species) and 99,135 individuals were identified region-wide. Polychaetes, crustaceans and molluscs were the dominant taxa, both by percent abundance (59%, 17%, 12% respectively) and percent species (44%, 25%, 17%, respectively). There were no major differences in the percent composition of benthic communities among states or between NMSs and corresponding non-sanctuary sites. Densities averaged 3,788 m-2, about 30% of the average density for West Coast estuaries. Mean density of benthic fauna in the present offshore survey, averaged by state, was highest in CA (4,351 m-2) and lowest in OR (2,310 m-2). Mean densities were slightly higher at NMS stations vs. non-sanctuary stations for both the CA and OR/WA regions. The 10 most abundant taxa were the polychaetes Mediomastus spp., Magelona longicornis, Spiophanes berkeleyorum, Spiophanes bombyx, Spiophanes duplex, and Prionospio jubata; the bivalve Axinopsida serricata, the ophiuroid Amphiodia urtica, the decapod Pinnixa occidentalis, and the ostracod Euphilomedes carcharodonta. Mediomastus spp. and A. serricata were the two most abundant taxa overall. Although many of these taxa have broad geographic distributions throughout the region, the same species were not ranked among the 10 most abundant taxa consistently across states. The closest similarities among states were between OR and WA. At least half of the 10 most abundant taxa in NMSs were also dominant in corresponding nonsanctuary waters. Many of the abundant benthic species have wide latitudinal distributions along the West Coast shelf, with some species ranging from southern CA into the Gulf of Alaska or even the Aleutians. Of the 39 taxa on the list of 50 most abundant taxa that could be identified to species level, 85% have been reported at least once from estuaries of CA, OR, or WA exclusive of Puget Sound. Such broad latitudinal and estuarine distributions are suggestive of wide habitat tolerances. Thirteen (1.2%) of the 1,108 identified species are nonindigenous, with another 121 species classified as cryptogenic (of uncertain origin), and 208 species unclassified with respect to potential invasiveness. Despite uncertainties of classification, the number and densities of nonindigenous species appear to be much lower on the shelf than in the estuarine ecosystems of the Pacific Coast. Spionid polychaetes and the ampharetid polychaete Anobothrus gracilis were a major component of the nonindigenous species collected on the shelf. NOAA’s five NMSs along the West Coast of the U.S. appeared to be in good ecological condition, based on the measured indicators, with no evidence of major anthropogenic impacts or unusual environmental qualities compared to nearby nonsanctuary waters. Benthic communities in sanctuaries resembled those in corresponding non-sanctuary waters, with similarly high levels of species richness and diversity and low incidence of nonindigenous species. Most oceanographic features were also similar between sanctuary and non-sanctuary locations. Exceptions (e.g., higher concentrations of some nutrients in sanctuaries along the CA coast) appeared to be attributable to natural upwelling events in the area at the time of sampling. In addition, sediments within the sanctuaries were relatively uncontaminated, with none of the samples having any measured chemical in excess of ERM values. The ERL value for chromium was exceeded in sediments at the OCNMS, but at a much lower percentage of stations (four of 30) compared to WA and OR non-sanctuary areas (31 of 70 stations). ERL values were exceeded for arsenic, cadmium, chromium, 2- methylnaphthalene, low molecular weight PAHs, total DDT, and 4,4′-DDE at multiple sites within the CINMS. However, cases where total DDT, 4,4′-DDE, and chromium exceeded the ERL values were notably less prevalent at CINMS than in non-sanctuary waters of CA. In contrast, 2-methylnaphthalene above the ERL was much more prevalent in sediments at the CINMS compared to non-sanctuary waters off the coast of CA. While there are natural background sources of PAHs from oil seeps throughout the SCB, this does not explain the higher incidence of 2-methylnaphthalene contamination around CINMS. Two stations in CINMS also had levels of TOC (> 5%) potentially harmful to benthic fauna, though none of these sites exhibited symptoms of impaired benthic condition. This study showed no major evidence of extensive biological impacts linked to measured stressors. There were only two stations, both in CA, where low numbers of benthic species, diversity, or total faunal abundance co-occurred with high sediment contamination or low DO in bottom water. Such general lack of concordance suggests that these offshore waters are currently in good condition, with the lower-end values of the various biological attributes representing parts of a normal reference range controlled by natural factors. Results of multiple linear regression, performed using full model procedures to test for effects of combined abiotic environmental factors, suggested that latitude and depth had significant influences on benthic variables regionwide. Latitude had a significant inverse influence on all three of the above benthic variables, i.e. with values increasing as latitude decreased (p< 0.01), while depth had a significant direct influence on diversity (p < 0.001) and inverse effect on density (p <0.01). None of these variables varied significantly in relation to sediment % fines (at p< 0.1), although in general there was a tendency for muddier sediments (higher % fines) to have lower species richness and diversity and higher densities than coarser sediments. Alternatively, it is possible that for some of these sites the lower values of benthic variables reflect symptoms of disturbance induced by other unmeasured stressors. The indicators in this study included measures of stressors (e.g., chemical contaminants, eutrophication) that are often associated with adverse biological impacts in shallower estuarine and inland ecosystems. However, there may be other sources of humaninduced stress in these offshore systems (e.g., bottom trawling) that pose greater risks to ambient living resources and which have not been captured. Future monitoring efforts in these offshore areas should include indicators of such alternative sources of disturbance. (137pp.) (PDF contains 167 pages)

Developing effective restoration plans to tackle the widespread impairment of coastal swimming and shellfishing waters

Congress established a legal imperative to restore the quality of our surface waters when it enacted the Clean Water Act in 1972. The act requires that existing uses of coastal waters such as swimming and shellfishing be protected and restored. Enforcement of this mandate is frequently measured in terms of the ability to swim and harvest shellfish in tidal creeks, rivers, sounds, bays, and ocean beaches. Public-health agencies carry out comprehensive water-quality sampling programs to check for bacteria contamination in coastal areas where swimming and shellfishing occur. Advisories that restrict swimming and shellfishing are issued when sampling indicates that bacteria concentrations exceed federal health standards. These actions place these coastal waters on the U.S. Environmental Protection Agencies’ (EPA) list of impaired waters, an action that triggers a federal mandate to prepare a Total Maximum Daily Load (TMDL) analysis that should result in management plans that will restore degraded waters to their designated uses. When coastal waters become polluted, most people think that improper sewage treatment is to blame. Water-quality studies conducted over the past several decades have shown that improper sewage treatment is a relatively minor source of this impairment. In states like North Carolina, it is estimated that about 80 percent of the pollution flowing into coastal waters is carried there by contaminated surface runoff. Studies show this runoff is the result of significant hydrologic modifications of the natural coastal landscape. There was virtually no surface runoff occurring when the coastal landscape was natural in places such as North Carolina. Most rainfall soaked into the ground, evaporated, or was used by vegetation. Surface runoff is largely an artificial condition that is created when land uses harden and drain the landscape surfaces. Roofs, parking lots, roads, fields, and even yards all result in dramatic changes in the natural hydrology of these coastal lands, and generate huge amounts of runoff that flow over the land’s surface into nearby waterways. (PDF contains 3 pages)

^(18)O/^(16)O and D/H studies on the interactions between heated meteoric ground waters and igneous intrusions: Western San Juan Mountains, Colorado and the Isle of Skye, Scotland

Detailed oxygen, hydrogen and carbon isotope studies have been carried out on igneous and metamorphic rocks of the Stony Mountain complex, Colorado, and the Isle of Skye, Scotland, in order to better understand the problems of hydrothermal meteoric water-rock interaction.

The Tertiary Stony Mountain stock (~1.3 km in diameter), is composed of an outer diorite, a main mass of biotite gabbro, and an inner diorite. The entire complex and most of the surrounding country rocks have experienced various degrees of ¹⁸O depletion (up to 10 per mil) due to interaction with heated meteoric waters. The inner diorite apparently formed from a low-¹⁸O magma with δ¹⁸O ≃ +2.5, but most of the isotopic effects are a result of exchange between H₂O and solidified igneous rocks. The low-¹⁸O inner diorite magma was probably produced by massive assimilation and/or melting of hydrothermally altered country rocks. The δ¹⁸O values of the rocks generally increase with increasing grain size, except that quartz typically has δ¹⁸O = +6 to +8, and is more resistant to hydrothermal exchange than any other mineral studied. Based on atom % oxygen, the outer diorites, gabbros, and volcanic rocks exhibit integrated water/rock ratios of 0.3 ± 0.2, 0.15 ± 0.1, and 0.2 ± 0.1, respectively. Locally, water/rock ratios attain values greater than 1.0. Hydrogen isotopic analyses of sericites, chlorites, biotites, and amphiboles range from -117 to -150. δD in biotites varies inversely with Fe/Fe+Mg, as predicted by Suzuoki and Epstein (1974), and positively with elevation, over a range of 600 m. The calculated δD of the mid-to-late-Tertiary meteoric waters is about -100. Carbonate δ¹³C values average -5.5 (PDB), within the generally accepted range for deep-seated carbon.

Almost all the rocks within 4 km of the central Tertiary intrusive complex of Skye are depleted in ¹⁸O. Whole-rock δ¹⁸O values of basalts (-7. 1 to +8.4), Mesozoic shales (-0.6 to + 12.4), and Precambrian sandstones (-6.2 to + 10.8) systematically decrease inward towards the center of the complex. The Cuillin gabbro may have formed from a ¹⁸O-depleted magma (depleted by about 2 per mil); δ¹⁸O of plagioclase (-7.1 to + 2.5) and pyroxene (-0.5 to + 3.2) decrease outward toward the margins of the pluton. The Red Hills epigranite plutons have δ¹⁸O quartz (-2.7 to + 7.6) and feldspar (-6.7 to + 6.0) that suggest about 3/4 of the exchange took place at subsolidus temperatures; profound disequilibrium quartz-feldspar fractionations (up to 12) are characteristic. The early epigranites were intruded as low-¹⁸O melts (depletions of up to 3 per mil) with δ¹⁸O of the primary, igneous quartz decreasing progressively with time. The Southern Porphyritic Epigranite was apparently intruded as a low-¹⁸O magma with δ¹⁸O ≃ -2.6. A good correlation exists between grain size and δ¹⁸O for the unique, high-¹⁸O Beinn an Dubhaich granite which intrudes limestone having a δ¹⁸O range of +0.5 to +20.8, and δ¹³C of -4.9 to -1.0. The δD values of sericites (-104 to -107), and amphiboles, chlorites, and biotites (-105 to -128) from the igneous rocks , indicate that Eocene surface waters at Skye had δD ≃ -90. The average water/rock ratio for the Skye hydrothermal system is approximately one; at least 2000 km³ of heated meteoric waters were cycled through these rocks.

Thus these detailed isotopic studies of two widely separated areas indicate that (1) ¹⁸O-depleted magmas are commonly produced in volcanic terranes invaded by epizonal intrusions; (2) most of the ¹⁸O-depletion in such areas are a result of subsolidus exchange (particularly of feldspars); however correlation of δ¹⁸O with grain size is generally preserved only for systems that have undergone relatively minor meteoric hydrothermal exchange; (3) feldspar and calcite are the minerals mos t susceptible to oxygen isotopic exchange, whereas quartz is very resistant to oxygen isotope exchange; biotite, magnetite, and pyroxene have intermediate susceptibilities; and (4) basaltic country rocks are much more permeable to the hydrothermal convective system than shale, sandstone, or the crystalline basement complex.

An approach to the use of macrophytes for monitoring standing waters

Under the EC Water Framework Directive (WFD), each Member State is required to devise a comprehensive national monitoring programme for surface waters, incorporating hydromorphological, physico-chemical and biological elements. This paper describes one aspect of the biota - the macrophyte flora - to classify standing waters and to monitor their water quality. The evolution of this method is described and suggestions for its future development are made.

Environmental quality standards to protect identified uses of controlled waters: salmonid fisheries, cyprinid fisheries, migratory fisheries, commercial harvesting of marine fish for public consumption, commercial harvesting of shellfish for for public consumption

This report considers the development of environmental quality standards (EQSs) for the salmonid fishery, cyprinid fishery, migratory fishery, commercial harvesting of marine fish for public consumption and commercial harvesting of shellfish for public consumption uses of controlled surface waters. Previous reports have been used to identify those parameters necessary for the maintenance of these five uses. Each water use is considered in a separate section within which identified parameters are discussed and standards proposed, a summary of the proposed standards is presented at the beginning of the relevant section. For salmonid, cyprinid and migratory fisheries, EQSs for substances in water have been proposed for the protection of these fisheries. For the commercial harvesting of marine fish and shellfish for public consumption uses 'Warning Levels' of substances in waters have been proposed. These 'Warning Levels' have been proposed by considering data on bioaccumulation and food standards and aim to prevent acceptable intake values and concentrations in fish/shellfish flesh exceeding statutory or recommended levels. For the commercial harvesting of marine fish for public consumption it has been concluded that the current EQSs for most List II substances for the protection of salt water life should be adequately stringent to protect this use, however for the commercial harvesting of shellfish for public consumption, these List II EQSs do not appear adequate to protect this use and more stringent 'Warning Levels' have been proposed. For all five uses considered in this report there has been found to be limited information on a number of the parameters considered and in general for indigenous species, this has been found to be especially so when considering migratory fisheries and the commercial harvesting of marine fish and shellfish.

Circulation pattern of the Egyptian Mediterranean waters during winter and summer seasons

The water circulation of the Egyptian Mediterranean waters was computed during winter and summer seasons using the dynamic method. The reference level was set at the 1000db surface. The results showed that the surface circulation is dominated by the Atlantic water inflow along the North African coast and by two major gyres, the Mersa Matruth anticyclonic gyre and El-Arish cyclonic gyre. The results showed a seasonal reversal of El-Arish gyre, being cyclonic in winter and anticyclonic in summer. El-Arish gyre had not been previously measured. The geostrophic current velocity at the edges of the Mersa Matruth gyre varied between 12.5 and 29.1cm/sec in winter and between 6.5 and 13.1cm/sec in summer. The current velocity reached its maximum values (>40cm/sec) at El-Arish gyre. The current velocity at the two gyres decreased with increasing depth. The North African Current affects the surface waters down to a depth of 100m, and that its mean velocity varies between 6 and 38cm/sec.

Radiolarian distribution in surface sediments of the northern and central South China Sea

Radiolarian distribution in surface sediments of 104 stations from northern and central South China Sea show that the abundance and diversity of radiolarians increase with the water depth and are related to radiolarian concentrations from the water column, diminished terrigenous input, variability in calcareous shell content and the rate of silica and carbonate dissolution in the deep sea. According to the appearances of individual species in surface sediments at particular depths, seven faunal boundaries distribution are recognized at water depths of 100, 450, 650, 1000, 1200, 1400 and 2500 m. Four radiolarian assemblages in the sediments were identified by applying clustering procedures. Geographic distributions of these four assemblages coincide with present-day hydrologic features of the surface waters in this area.

Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (delta(13)C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. delta(13)C values of both POC (-23.8parts per thousand to -26.8parts per thousand) and DOC (-25.0parts per thousand to -29.0parts per thousand) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in delta(13)C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-delta(13)C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-delta(13)C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10-30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted. (C) 2004 Elsevier B.V. All rights reserved.

Current status of bacteriological parameters and DOC/POC in Xiamen coastal waters

The surface and bottom waters samples were collected from six locations in Xiamen western sea. The quantified estimation of bacterial production (H-3-thymidine method) and observation of bacterial heterotrophic activity (C-14-glucose method) have been made in order to have a better understanding of the role of marine bacteria and their activities. The results showed that the mean value of bacterial heterotrophic activity was 9 X 10(8) cells/(L. h) in the surface waters and 2.6 X 10(8) cells/(L. h) in the bottom waters. The mean value of bacterial production was 38 X 108 cells/( L. h) in the surface waters and 7.1 X 10(8) cells/(L. h) in the bottom waters. The relationship between bacterial production, heterotrophic activity, PCC and DOC measured during this survey were discussed. The good understanding of the relationship between bacteria activity and total coliform was addressed.

Seasonal changes in the distribution of dissolved organic nitrogen in coastal and open-ocean waters in the North East Pacific: sources and sinks

The distribution of dissolved organic nitrogen (DON) and nitrate were determined seasonally (winter, spring and summer) during three years along line P, i.e. an E-W transect from the coast of British Columbia, Canada, to Station P (50degreesN, 145degreesW) in the subarctic North East Pacific Ocean. In conjunction, DON measurements were made in the Straits of Juan de Fuca and Georgia within an estuarine system connected to the NE Pacific Ocean. The distribution of DON at the surface showed higher values of 4-17 muM in the Straits relative to values of 4-10 muM encountered along line P, respectively. Along line P, the concentration of DON showed an inshore-offshore gradient at the surface with higher values near the coast. The equation for the conservation of DON showed that horizontal transport of DON (inshore-offshore) was much larger than vertical physical mixing. Horizontal advection of DON-rich waters from the coastal estuarine system to the NE Pacific Ocean was likely the cause of the inshore-offshore gradient in the concentration of DON. Although the concentration of DON was very variable in space and time, it increased from winter to summer, with an average build up of 4.3 muM in the Straits and 0.7 muM in the NE subarctic Pacific. This implied seasonal DON sources of 0.3 mmol N m(-2) d(-1) at Station P and 1.5 mmol N m(-2) d(-1) in the Straits, respectively. These seasonal DON accumulation rates corresponded to about 15-20% of the seasonal nitrate uptake and suggested that there was a small seasonal build up of labile DON at the surface. However, the long residence times of 180-1560 d indicated that the most of the DON pool in surface waters was refractory in two very different productivity regimes of the NE Pacific. (C) 2002 Elsevier Science Ltd. All rights reserved.

Covariance among North Sea ecosystem state indicators during the past 50 years - contrasts between coastal and open waters

Regime shift and principal component analysis of a spatially disaggregated database capturing time-series of climatic, nutrient and plankton variables in the North Sea revealed considerable covariance between groups of ecosystem indicators. Plankton and climate time-series span the period 1958–2003, those of nutrients start in 1980. In both regions, the period from 1989 to 2001 identified in principal component 1 had warmer surface waters, higher Atlantic inflow and stronger winds, than the periods before or after. However, it was preceded by a regime shift in both open (PC2) and coastal (PC3) waters during 1977 towards more hours of sunlight and higher water temperature, which lasted until 1997. The relative influence of nutrient availability and climatic forcing differed between open and coastal North Sea regions. Inter-annual variability in phytoplankton dynamics of the open North Sea was primarily regulated by climatic forcing, specifically by sea surface temperature, Atlantic inflow and co-varying wind stress and NAO. Coastal phytoplankton variability, however, was regulated by insolation and sea surface temperature, as well as Si availability, but not by N or P. Regime shifts in principal components of hydrographic and climatic variables (explaining 55 and 61% of the variance in coastal and open water variables) were detected using Rodionov's sequential t-test. These shifts in hydroclimatic variables which occurred around 1977, 1989, 1997 and 2001, were synchronized in open and coastal waters, and were tracked by open water chlorophyll and copepods, but not by coastal plankton. North–central–south or open-coastal spatial breakdowns of the North Sea explained similar amounts of variability in most ecosystem indicators with the exception of diatom abundance and chlorophyll concentration, which were clearly better explained using the open-coastal configuration.

Annual study of oxygenated volatile organic compounds in UK shelf waters

We performed an annual study of oxygenated volatile organic compound (OVOC) seawater concentrations at a site off Plymouth, UK in the Western English Channel over the period of February 2011–March 2012. Acetone concentrations ranged from 2–10 nM (nanomole/L) in surface waters with a maximum observed in summer. Concentrations correlated positively with net shortwave radiation and UV light, suggestive of photochemically linked acetone production. We observed a clear decline in acetone concentrations below the mixed layer. Acetaldehyde varied between 4–37 nM in surface waters with higher values observed in autumn and winter. Surface concentrations of methanol ranged from 16–78 nM, but no clear annual cycle was observed. Methanol concentrations exhibited considerable inter-annual variability. We estimate consistent deposition to the sea surface for acetone and methanol but that the direction of the acetaldehyde flux varies during the year.

An Integrated Approach to Quantifying Groundwater and Surface Water Contributions of Stream Flow

The management of water resources in Ireland prior to the Water Framework Directive (WFD) has focussed on surface water and groundwater as separate entities. A critical element to the successful implementation of the
WFD is to improve our understanding of the interaction between the two and flow mechanisms by which groundwaters discharge to surface waters. An improved understanding of the contribution of groundwater to surface water is required for the classification of groundwater body status and the determination of groundwater quality thresholds. The results of the study will also have a wider application to many areas of the WFD.
A subcommittee of the WFD Groundwater Working Group (GWWG) has been formed to develop a methodology to estimate the groundwater contribution to Irish Rivers. The group has selected a number of analytical techniques to quantify components of stream flow in an Irish context (Master Recession Curve, Unit Hydrograph, Flood Studies Report methodologies and
hydrogeological analytical modelling). The components of stream flow that can be identified include deep groundwater, intermediate and overland. These analyses have been tested on seven pilot catchments that have a variety of hydrogeological settings and have been used to inform and constrain a mathematical model. The mathematical model used was the NAM (NedbØr-AfstrØmnings-Model) rainfall-runoff model which is a module of DHIs MIKE 11 modelling suite. The results from these pilot catchments have been used to develop a decision model based on catchment descriptors from GIS datasets for the selection of NAM parameters. The datasets used include the mapping of aquifers, vulnerability and subsoils, soils, the Digital Terrain Model, CORINE and lakes. The national coverage of the GIS datasets has allowed the extrapolation of the mathematical model to regional catchments across Ireland.

Integration of geochemical and biological modifications in mining areas: waters, sediments and diatoms

The development of mining activities over thousands of years in the region of Aljustrel is nowadays visible as a vast area of ore tailings, slag and host rocks of sulphides mineralization. The generation of acidic waters by the alteration of pyritic minerals - Acid Mine Drainage (AMD) - causes a significant impact on the river system both in the south of the village (Rib ª. Água Forte) and in the north of it (Rib ª. Água Azeda and Barranco do Farrobo), which is reflected in extremely low pH values (< 3) and high concentrations of As, Cd, Cu, Fe, Mn, Pb, Zn and sulphates. This study aimed to assess the environmental impacts extent, integrating geochemical (surface waters and stream sediments) and biological (diatoms) parameters. Three groups of sites were defined, based on sediments and water analysis, which integration with diatom data showed the same association of groups: Group 1- impacted, with acidic pH (1.9-5.1), high metal contents (0.4-1975 mg L-1) and Fe-Mg-sulphate waters, being metals more bioavailable in waters in cationic form (Me2+); mineralogically the sediments were characterized by phyllosilicates and sulphates/oxy-hydroxysulphate phases, easily solubilized, retaining a high amount of metals when precipitated; dominant taxon was Pinnularia aljustrelica (a new species); Group 2- slightly impacted, weak acid to neutral pH (5.0-6.8), metal contents not so high (0.2-25 mg L-1) and Fe-Mg-sulphate to Mg-chloride waters; dominant taxa were Brachysira neglectissima and Achnanthidium minutissimum; Group 3- unimpacted, alkaline pH (7.0-8.4), low metal contents (0-7 mg L-1) with Mg-chloride waters. In this group, metals were associated to the primary phases (e.g. sulphides), not so easily available; the existence of high chloride contents explained the presence of typical taxa of brackish/marine (e.g. Entomoneis paludosa) waters. Taxonomical aspects of the diatoms were studied (discovery of a new species: Pinnularia aljustrelica Luis, Almeida et Ector sp. nov.), as well as morphometric (size decrease of diatoms valves, as well as the appearance of deformed valves of Eunotia exigua in Group 1 and A. minutissimum in Group 2) and physiological (effective to assess the effects of metals/acidity in the photosynthetic efficiency through PAM Fluorometry) aspects. A study was carried out in an artificial river system (microcosm) that aimed to mimic Aljustrel’s extreme conditions in controlled laboratory conditions. The chronic effects of Fe, SO42- and acidity in field biofilms, inoculated in the artificial rivers, were evaluated as well as their contribution to the communities’ tolerance to metal toxicity, through acute tests with two metals (Cu and Zn). In general, the effects caused by low pH values and high concentrations of Fe and SO42- were reflected at the community level by the decrease in diversity, the predominance of acidophilic species, the decrease in photosynthetic efficiency and the increase of enzymatic (e.g. catalase, superoxide dismutase) and non-enzymatic activities (e.g. total glutathione and total phytochelatins). However, it was possible to verify that acidity performed a protective effect in the communities, upon Cu and Zn addition. A comparative study between Aljustrel mining area and New Brunswick mining area was carried out, both with similar mining and geological conditions, reflected in similar diatom communities in both mines, but in very different geographic and climatic areas.