Bioavailability of metals along a contamination gradient in San Diego Bay (California, USA)

San Diego Bay is heavily contaminated with metals, but little is known about their biological availability to local marine organisms. This study on 15 elements showed that concentrations of metals associated with sediment increased from the mouth to the back of the Bay while metals in seawater particulates were similar throughout the Bay. Metal bioavailability was assessed over 8weeks following transplant of the local brittlestar, Ophiothrix spiculata (Ophuroidea, Echinodermata), from outside to inside the Bay. Despite a gradient of contamination, brittlestars accumulated similar levels of metals throughout the Bay, suggesting that metal contamination occurred through dissolved metals as well as through the diet. Sediment transplanted in dialysis tubing in the Bay accumulated metals only when placed on the seafloor bottom, indicating greater metal bioavailability near the bottom; the level of accumulation was similar between the mouth and the back of the Bay. The results are consistent with a circulation pattern in which a bottom layer of seawater, enriched with metals, drains from the back to the mouth of the Bay. There was a positive correlation between metal concentration in brittlestars and tidal range, suggesting increased metal exposure due to bay-ocean water exchange. For brittlestar arms the correlation was higher at the mouth than the back of the Bay, indicating greater metal accumulation in arms from dissolved metals in seawater than from ingestion of metal contaminated diet. In contrast, for brittlestar disks the correlation was higher at the back of the Bay, indicative of metal accumulation mainly through the diet. The results highlight the importance of considering bioavailability and physical processes in environmental quality assessments.     

Sustainable farming practices of the Chinese mitten crab (<Emphasis Type="Italic">Eriocheir sinensis)</Emphasis> around Hongze Lake,lower Yangtze River Basin,China

Results of a survey of 156 Chinese mitten crab (Eriocheir sinensis) grow-out farms around Hongze Lake (118.48–118.72°E; 33.36–33.38°N) are reported. Area farmed has remained relatively unchanged but production (59 932 t in 2012) increased steadily over the last 7 years, indicative of the viability and sustainability of the farming system that has gradually replaced intensive Chinese major carp polyculture around Hongze Lake. Results showed that production range was 135–2400 kg ha⁻¹ cycle⁻¹ (mean 1144 ± 34). Crab yields correlated linearly to stocking density and conformed to a normal distribution curve, with 66.7 % of farms yielding 900 kg ha⁻¹ cycle⁻¹ or more. Yield was negatively correlated to pond size and capture size (p < 0.01), and farms with macrophyte coverage rate lower than 30 % of water surface were significantly (p < 0.05) lower than those exceeding 30 %.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-015-0722-0) contains supplementary material, which is available to authorized users.     

Seasonal variations and trends in concentrations of filter-collected polycyclic aromatic hydrocarbons (PAH) and mutagenic activity in the San Francisco Bay area

Air monitoring in the San Francisco Bay Area was carried out to measure outdoor community air concentrations of polycyclic aromatic hydrocarbons (PAH) and mutagenic activity (mutagenicity) in particulate organic matter (POM). Monitoring began in 1979 and is currently conducted at six stations. PAH and mutagenicity tests were performed on organic extracts prepared from high volume (hi-vol) filters composited every four months, by meterological season. PAH were determined by high pressure liquid chromatography (HPLC) with fluorescence and ultraviolet detection. Mutagenicity was measured in the Ames Salmonella bioassay using strain TA98 with and without metabolic activation. The nine-year mean concentration of benzo(a)pyrene (BaP) was 0.4 ng/m3. The mutagenicity of this amount of BaP accounted for only about 0.2% of the observed mutagenicity in POM and other measured PAH accounted for even less. Concentrations of PAH and mutagenicity were three to nine times higher during the winter than during other seasons. Year-to-year wintertime trends in several PAH were also seen. Early in the 1980s, winter concentrations of BaP and benzo (g,h,i)perylene increased. However since the mid-1980's, their concentrations have fallen. The decrease in PAH concentrations may be the result of an increasing proportion of vehicles with relatively low organic emissions. In contrast to PAH, mutagenicity did not show significantly year-to-year time trends.     

Comparisons of EPA Rollback,Empirical/Kinetic,and Physicochemical Oxidant Prediction Relationships in the San Francisco Bay Area

This paper describes, compares and evaluates selected Oxidant Prediction Relationships {OPRs) in terms of projections of hydrocarbon emission reductions required for attainment of the former 0.08 ppm standard and the new 0.12 ppm standard in the San Francisco Bay Area in 1985. The OPRs analyzed are the LIRAQ physicochemical model, EPA’s Empirical Kinetic Modeling Approach (EKMA), linear and Appendix J rollback, and an empirical OPR based on local observations.

LIRAQ simulations indicated that to achieve the 0.12 ppm ozone standard, 1985 hydrocarbon emissions must be reduced by 27% from projected levels. The equivalent reductions derived from simple linear rollback, linear rollback with 0.04 ppm background, and the local empirical OPR were 32%, 45% and 37%, respectively. The LIRAQ simulations also showed that reduction of both hydrocarbon and NO_x emissions is less effective than reduction of hydrocarbons only. The attempt to apply EKMA failed because the Bay Area’s low hydrocarbon/NO_x ratios and observed ozone levels are not consistent with the standard EKMA isopleth curves.

For planning, proper OPR selection is important because the wide range in the projections of various OPRs translates into a correspondingly wide range in control costs. Physicochemical OPRs are preferred because they are verifiable; they account for complex topography, meteorology, and source distributions; and because they can treat a variety of control strategies. In the future, the uncertainties associated with the projections can be resolved by assessing trends in air quality on a regular basis and by upgrading and reapplying the prediction methodologies as new information becomes available.     

Morphological, biochemical, and histopathological indices and contaminant burdens of cotton rats (Sigmodon hispidus) at three hazardous waste sites near Houston, Texas, USA

Male cotton rats (Sigmodon hispidus) were studied at three industrial waste sites near Houston, Texas, to determine whether various morphological, biochemical, and histopathological indices provided evidence of contaminant exposure and toxic insult. Only modest changes were detected in cotton rats residing at waste sites compared with reference sites. No single parameter was consistently altered, except hepatic cytochrome P-450 concentration which was lower ( [Formula: see text] ) at two waste sites, and tended to be lower ( [Formula: see text] ) at a third waste site. Elevated petroleum hydrocarbon concentrations were detected in rats at one waste site, but contaminant burdens of rats from the other sites were unremarkable. Unlike rats captured in summer, those trapped in winter exhibited hepatocellular hypertrophy and up to a 65% increase in liver: body weight ratio, cytochrome P-450 concentration, and activities of aniline hydroxylase, aryl hydrocarbon hydroxylase, and glutathione S-transferase. Although genotoxicity has been previously documented in cotton rats residing at two of the waste sites, biomarkers in the present study provided little evidence of exposure and damage.     

Ozone distribution and phytotoxic potential in mixed conifer forests of the San Bernardino Mountains, southern California

In the San Bernardino Mountains of southern California, ozone (O(3)) concentrations have been elevated since the 1950s with peaks reaching 600ppb and summer seasonal averages >100ppb in the 1970s. During that period increased mortality of ponderosa and Jeffrey pines occurred. Between the late 1970s and late1990s, O(3) concentrations decreased with peaks approximately 180ppb and approximately 60ppb seasonal averages. However, since the late 1990s concentrations have not changed. Monitoring during summers of 2002-2006 showed that O(3) concentrations (2-week averages) for individual years were much higher in western sites (58-69ppb) than eastern sites (44-50ppb). Potential O(3) phytotoxicity measured as various exposure indices was very high, reaching SUM00 - 173.5ppmh, SUM60 - 112.7ppmh, W126 - 98.3ppmh, and AOT40 - 75ppmh, representing the highest values reported for mountain areas in North America and Europe.     

Irrigation runoff insecticide pollution of rivers in the Imperial Valley, California (USA)

The Alamo and New Rivers located in the Imperial Valley, California receive large volumes of irrigation runoff and discharge into the ecologically sensitive Salton Sea. Between 1993 and 2002 we conducted a series of studies to assess water quality using three aquatic species: a cladoceran (Ceriodaphnia dubia), a mysid (Neomysis mercedis), and a larval fish (Pimephales promelas). Although no mortality was observed with the P. promelas, high-level toxicity to the invertebrate species was documented in samples from both rivers during many months of each year. Toxicity identifications and chemical analyses identified the organophosphorus insecticides (OP), chlorpyrifos and diazinon, as the cause of C. dubia toxicity. The extent of the C. dubia mortality was highly correlated with quantities of these OPs applied in the river watersheds. C. dubia mortality occurred during more months of our 2001/2002 study than in the 1990s investigations. During 2001/2002, the extensive C. dubia mortality observed in New River samples was caused by OP insecticide pollution that originated from Mexico. Mortality to N. mercedis in New River samples was likely caused by contaminants other than OP insecticides. Our studies document OP insecticide-caused pollution of the Alamo River over a 10-year period and provide the necessary information for remediation efforts.     

Relationships of ozone exposure to pine injury in the Sierra Nevada and San Bernardino Mountains of California, USA

Hourly ambient ozone exposure data and crown injury measurements were gathered in the Sierra Nevada and San Bernardino Mountains of California to develop relationships between the Ozone Injury Index (OII), the Forest Pest Management Index (FPM), chlorotic mottle, fascicle retention (OII index components) and cumulative ambient ozone indices for Pinus ponderosa Dougl. ex Laws and Pinus jeffreyi Grev. and Balf. Eleven sites located in the mixed conifer forest near ambient ozone monitoring sites were evaluated annually for 4 years. Four other sites in the San Bernardino Mountains were evaluated for 1 year. Analyses showed OII to be functionally equivalent (r2 = 0.96) to the FPM, and to depend only on fascicle retention and chlorotic mottle (R2 = 0.95) of the fourth whorl (or if four whorls are not present at the site, then the last whorl present for the majority of trees). Significant associations were found between OII and 4-year 24-h. summer SUM0, SUM06, W126 and HRS80 ozone indices. Three sites had higher levels of cumulative chlorotic mottle for individual whorls and larger numbers of trees with visible crown injury than other sites with similar cumulative ambient ozone levels. Including an indicator variable to discriminate between these two groups of sites increased R2 and decreased root mean square (RMSE) for all indices, especially SUM0 (R2 = 0.93, RMSE reduced by 46%).     

Integrated assessment of the impacts of agricultural drainwater in the Salinas River (California,USA)

The Salinas River is the largest of the three rivers that drain into the Monterey Bay National Marine Sanctuary in central California. Large areas of this watershed are cultivated year-round in row crops and previous laboratory studies have demonstrated that acute toxicity of agricultural drainwater to Ceriodaphnia dubia is caused by the organophosphate (OP) pesticides chlorpyrifos and diazinon. In the current study, we used a combination of ecotoxicologic tools to investigate incidence of chemical contamination and toxicity in waters and sediments in the river downstream of a previously uncharacterized agricultural drainage creek system. Water column toxicity was investigated using a cladoceran C. dubia while sediment toxicity was investigated using an amphipod Hyalella azteca. Ecological impacts of drainwater were investigated using bioassessments of macroinvertebrate community structure. The results indicated that Salinas River water downstream of the agricultural drain is acutely toxic to Ceriodaphnia, and toxicity to this species was highly correlated with combined toxic units (TUs) of chlorpyrifos and diazinon. Laboratory tests were used to demonstrate that sediments in this system were acutely toxic to H. azteca, which is a resident genus. Macroinvertebrate community structure was moderately impacted downstream of the agricultural drain input. While the lowest macroinvertebrate abundances were measured at the station demonstrating the greatest water column and sediment toxicity and the highest concentrations of pesticides, macroinvertebrate metrics were more significantly correlated with bank vegetation cover than any other variable. Results of this study suggest that pesticide pollution is the likely cause of laboratory-measured toxicity in the Salinas River samples and that this factor may interact with other factors to impact the macroinvertebrate community in the system.     

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics?+?pyrogenics) was 250.6?±?73.7 ng g^?1 dw; biogenic PAH constituted 67?±?4 % of total PAH. THC were 26?±?9 % of total biogenic PAH, THP were 36?±?7 %, and perylene was 38?±?7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60–93 % of total PAH; THC, THP and perylene were 31?±?28 %, 24?±?32 %, and 45?±?36 % of biogenic PAH. At 100–103 cm depth, THP constituted 80 % of biogenic PAH and at 120–123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river’s watershed.     

Butyltins in shellfish, finfish, water and sediment from the Coos Bay estuary (Oregon, USA)

Butyltin was measured in tissue, water and sediment samples collected throughout Coos Bay estuary between 1986 and 1997. Butyltin-induced shell deformation in commercial oysters prompted this assessment. Butyltins are released from tributyltin oxide (TBTO)-containing boat paint. Clams from three sites contained tributyltin (TBT) levels ranging from 168 to 457 microg/kg in 1992-1994. Consequently, Oregon Health Division (OHD) issued a shellfish consumption advisory in 1995; it was rescinded in 1997 after US Environmental Protection Agency (EPA) revised the TBTO oral reference dose (RfD). The revised RfD changed the tissue screening level from 112 to 1120 microg TBT/kg. Fifty percent of sediment samples collected during 1991-1997 and analyzed for total butyltins (TotBT) exceeded the Puget Sound Dredge Disposal Analysis Screening Level (PSDDA SL) of 73 microg TBT/kg dw. TotBT at three shipyards selected for site assessment by EPA ranged from 24 to 68,613 microg/kg dw. Sediment and tissue butyltins have been decreasing in all but one area of the estuary.     

Polycyclic aromatic hydrocarbons in the San Francisco Estuary water column: sources, spatial distributions, and temporal trends (1993-2001)

The composition of PAH in surface waters was examined over a range of spatial and temporal scales to determine distributions, trends, and possible sources. Water samples were collected from 1993 to 2001. PAH in organic extracts were analyzed by gas chromatography-mass spectrometry (GC-MS) and 25 individual target PAH summed to get the total PAH concentration in each water sample. The distribution of median total PAH concentration by estuary segments was Extreme South Bay (120 ng l(-1)) > South Bay (49 ng l(-1)) > North Estuary (29 ng l(-1)) > Central Bay (12 ng l(-1)) > Delta (7 ng l(-1)). Overall, total PAH concentrations were significantly higher in the Extreme South Bay compared to all other segments, and the Central Bay and Delta were significantly lower than all other segments (Kruskal-Wallis, H = 157.27, df = 4, p < 0.0005). This distribution reflects the large urbanized and industrialized areas that border the southern portions of the estuary and the less populated and rural areas that surround the Delta. Temporal trend analysis showed a statistically significant temporal trend in total PAH concentration at only one of the 18 sampling stations situated throughout the estuary (San Jose, significant decrease, p = 0.031, r(2) = 0.386, n = 12). PAH isomer pair ratio analysis showed that PAH in estuary waters were derived primarily from combustion of fossil fuels/petroleum (possible PAH source contributors include coal, gasoline, kerosene, diesel, No. 2 fuel oil, and crude oil) and biomass (possible contributors include wood and grasses), with lesser amounts of PAH contributed from direct petroleum input.     

Mercury methylation by a microbial community from sediments of the Adour Estuary (Bay of Biscay, France)

In order to study the influence of microorganisms on the mercury biogeochemistry, the metal content and the structure of microbial communities were determined in sediments from stations along the Adour Estuary. The comparison of the bacterial communities and their distribution in function of the environmental parameters by Canonical Correspondence Analysis (CCA) revealed the influence of metals on the bacterial communities structure. Sediments where the bacterial communities are mostly influenced by methylmercury were incubated in slurries with or without mercury, under oxic and anoxic conditions. Methylmercury production was detected in the anoxic biotic slurries with a net methylation yield of 0.3% after 24 h. CCA based on T-RFLP profiles revealed the impact of mercury addition on the bacterial communities structure. In addition, 17 bacterial strains, mainly sulphate-reducing bacteria involved in mercury methylation, were isolated and identified.     

Growth response of bigcone Douglas fir (Pseudotsuga macrocarpa) to long-term ozone exposure in southern California

Long-term radial growth of bigcone Douglas fir (Pseudotsuga macrocarpa) was studied throughout its range in the San Bernardino Mountains of southern California, where ambient ozone has been high for approximately the past 40 years. A gradient of both ozone concentration and precipitation exists from west (high) to east (low). Growth rates of bigcone Douglas fir are considerably lower since 1950 throughout the San Bernardino Mountains, with the largest growth reductions in the western part of the range where ozone exposure is highest. Needle retention is also somewhat lower at high ozone sites. Lower annual precipitation since 1950 may have some impact on long-term growth reductions, and short-term growth reductions induced by drought are an important component of long-term growth reductions at sites with high ozone exposure. An ozone-climate stress complex may be responsible for recent reductions in the growth of bigcone Douglas fir.     

Identifying primary stressors impacting macroinvertebrates in the Salinas River (California, USA): relative effects of pesticides and suspended particles

Laboratory dose-response experiments with organophosphate and pyrethroid pesticides, and dose-response experiments with increasing particle loads were used to determine which of these stressors were likely responsible for the toxicity and macroinvertebrate impacts previously observed in the Salinas River. Experiments were conducted with the amphipod Hyalella azteca, the baetid mayfly Procloeon sp., and the midge Chironomus dilutus (Shobanov, formerly Chironomus tentans). The results indicate the primary stressor impacting H. azteca was pesticides, including chlorpyrifos and permethrin. The mayfly Procloeon sp. was sensitive to chlorpyrifos and permethrin within the range of concentrations of these pesticides measured in the river. Chironomus dilutus were sensitive to chlorpyrifos within the ranges of concentrations measured in the river. None of the species tested were affected by turbidity as high as 1000 NTUs. The current study shows that pesticides are more important acute stressors of macroinvertebrates than suspended sediments in the Salinas River.     

Effects of oxidant air pollutants on western pine beetle (Coleoptera: Scolytidae) populations in southern California

The attack rates, brood survival, and emergence rates of the western pine beetle, Dendroctonus brevicomis LeConte, and incidence of entomophagus associates, were compared between photochemical oxidant damaged, and apparently healthy, ponderosa pine trees, Pinus ponderosa Dougl. ex Laws in the San Bernardino Forest in Southern California. The results from this study suggest that oxidant-damaged trees attacked by western pine beetle produced about the same total brood with lower initial attacks when compared with healthier trees, whereas the numbers of predators and parasitoids were higher in the healthier trees. This higher productivity trend for western pine beetle is most evident in trees attacked by the first beetle generation. Trees attacked by the second generation, both damaged and healthy, produced much less western pine beetle brood than generation 1 attacked trees, regardless of oxidant damage. The implication of these results is that, in stands with a higher proportion of oxidant damaged trees, a given population of western pine beetle could kill more trees, and increase at a greater rate, than in a stand with a lower proportion of damaged trees.     

Variability of indicator values for ozone production sensitivity: a model study in Switzerland and San Joaquin Valley (California)

The threshold values of indicator species and ratios delineating the transition between NO_x and VOC sensitivity of ozone formation are assumed to be universal by various investigators. However, our previous studies suggested that threshold values might vary according to the locations and conditions. In this study, threshold values derived from various model simulations at two different locations (the area of Switzerland by UAM Model and San Joaquin Valley of Central California by SAQM Model) are examined using a new approach for defining NO_x and VOC sensitive regimes. Possible definitions for the distinction of NO_x and VOC sensitive ozone production regimes are given. The dependence of the threshold values for indicators and indicator ratios such as NO_y, O₃/NO_z, HCHO/NO_y, and H₂O₂/HNO₃ on the definition of NO_x and VOC sensitivity is discussed. Then the variations of threshold values under low emission conditions and in two different days are examined in both areas to check whether the models respond consistently to changes in environmental conditions. In both cases, threshold values are shifted similarly when emissions are reduced. Changes in the wind fields and aging of the photochemical oxidants seem to cause the day-to-day variation of the threshold values. O₃/NO_z and HCHO/NO_y indicators are predicted to be unsatisfactory to separate the NO_x and VOC sensitive regimes. Although NO_y and H₂O₂/HNO₃ provide a good separation of the two regimes, threshold values are affected by changes in the environmental conditions studied in this work.     

Role of manganese oxides in the exposure of mute swans (Cygnus olor) to Pb and other elements in the Chesapeake Bay, USA

The aims of this study are to estimate exposure of waterfowl to elements in contaminated sediments in the Chesapeake Bay and to consider the potential role of Mn in influencing bioavailability and exposure. Metal concentrations were measured in livers and digesta taken from mute swans living on the Aberdeen Proving Ground, whose sediment had elevated concentrations of Cu, S, Se, Zn, As, Co, Cr, Hg and Pb. Concentrations of only the first four of these elements were elevated in swan digesta. None of the concentrations detected in the digesta or livers of the swans was considered toxic, although the concentrations of Cu and Se were high compared to concentrations of these elements reported in other waterfowl. Lead was found to be scavenged by Mn and Fe oxides from the water and deposited on the surface of vegetation at a reference site. Under some environmental chemical conditions, this is an important route of exposure to Pb in waterfowl, not previously recognized.     

Comparative bioavailability of trace metals using three filter-feeder organisms in a subtropical coastal environment (Southeast Gulf of California)

To evaluate the relative bioavailability of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the coastal waters of one selected site in Mazatlán Harbor, different filter feeder organisms, an oyster (Crassostrea corteziensis), a mussel (Mytella strigata) and a barnacle (Fistulobalanus dentivarians), were sampled during 1 year. Seasonal and interspecific variations in some metal concentrations were evident, especially for Cd, Ni, Pb and Zn. In contrast with Fe, Pb and Zn, the concentrations of Cd varied accordingly in both bivalves. Even though the organisms live in the same site and have a common feeding mechanism, accumulated body Cd concentrations were different. Mussels concentrated significantly higher levels of Ni than the other organisms, while barnacles were better concentrators of Cd, Pb and Zn. A relationship existed between the concentrations of Cd, Fe and Zn in the soft tissues of the two bivalves, which is useful in monitoring studies when only one species occurs.