联合基于野外的代谢组学和化学分析手段筛选优先关注新兴污染物：在五大湖流域的案例研究

由于毒性评估项目很难与日渐增长的需要测试的污染物保持同步,所以较难将关注点集中在影响水生生态系统的最为生物相关的污染物上。由于评估潜在毒性污染物所造成的生物影响已被证明是有效的,内生性代谢物的研究（代谢组学）对于剔除那些较低可能造成生物影响的污染物或许有一定帮助,从而找出生物重要性最高的污染物。本研究在北美五大湖流域的18个地点针对置于笼中的黑头软口鲦（Pimephales promelas）进行实验。我们测定了水体温度和水样中的污染物浓度（目标污染物132种,检出86种）,并使用1H-NMR谱测量了肝极性提取物中的内生性代谢物。利用偏最小二乘法回归来比对内生性代谢物的相对丰度与污染物浓度和环境温度。结果表明内生性极性代谢物的指标与最多49种污染物存在共同变化。因此我们认为至多52%的检出污染物与内生性代谢物变化的共同变化不显著,表明这些污染物很可能不会在这些地点造成可以检测到的影响。这是通过缩短对于实验地点有着潜在影响的污染物列表从而扫描出检出污染物生物相关性的第一步。类似的信息有助于风险评估者区分不同污染物的重要性并将重点毒性测试放在最为生物相关的污染物上。
精选自Nicol Janecko, Lucie Pokludova, Jana Blahova, Zdenka Svobodova, Ivan Literak. Linking field-based metabolomics and chemical analyses to prioritize contaminants of emerging concern in the Great Lakes basin. Environmental Toxicology and Chemistry: Volume 35, Issue 10, pages 2493–2502, October 2016. DOI: 10.1002/etc.3409
详情请见http://onlinelibrary.wiley.com/doi/10.1002/etc.3409/full
     

Transcriptional activation of plant defence genes by short-term air pollutant stress

The expression of defence genes was monitored by RNA blot analyses in tobacco plants (Nicotiana tabacum cv. SR-1) treated with various air pollutants at realistic concentrations that prevail in urban areas. Six-week-old plants responded with an increase in the steady-state mRNA levels of phenylalanine ammonia-lyase (PAL), chalcone synthase (CHS), chitinase and beta-1,3-glucanase, when exposed to defined and subnecrotic concentrations of automobile exhaust and/or ozone over a period of 48 h. An enhanced expression of genes encoding mitochondrial and cytosolic superoxide dismutases suggested that air pollutants induced considerable oxidative stress. Moreover, wounding or elicitor treatment of plants already exposed to automobile exhaust and/or ozone additionally increased the expression of the above defence genes, but not so in NO(2). Since the main difference between NO(2) and exhaust gas is the absence of the hydrocarbon compounds in the former, we regard hydrocarbons as favourite candidates for the toxic effect of exhaust gas, and they possibly act by generating an enhanced oxidative stress.     

Background Mercury Concentrations in River Water in Maine, U.S.A.

Mercury concentrations in 58 rivers in Maine was measured to range from below detection up to 7.01 ng L^-1 and averaged 1.80±1.29 ng L^-1. The concentration gradient for mercury in rivers across the state was not uniform. Mercury strongly correlated with dissolved organic carbon (DOC) and aluminum, and less strongly with copper, lead, and zinc. Mercuryexhibited significant differences in correlations with chemical variables and local geology when partitioned by flow state (high or low). Mercury concentrations were greatest in rivers flowingacross either wacke-type bedrock at low metamorphic grade, or glacial-till deposits. Elevated concentrations of mercury formed a locus in northern Maine under both high and low-flow states while in southwestern Maine a locus formed only during high-flowstates. These regional differences were statistically significantwhen compared by geographical location. We suggest that there is a bedrock source of mercury in northeastern Maine that is dilutedduring periods of high runoff. The elevated concentrations detected under high-flow states, as noted in southwestern Maine, may reflect mercury released from storage in association withDOC during periods of high runoff. The association of mercury with flow state indicates that watershed processes and local geology can modulate the concentration of mercury in rivers.     

Paleoecological Assessment of Watershed History in PRIMENet Watersheds at Acadia National Park, USA

Paleoecological reconstructions of forest stand histories for two upland watersheds at Acadia National Park in Maine were completed to support related watershed chemistry studies. The project hypothesis was that forest type and fire history influence long-term cycling and storage of atmospheric mercury and nitrogen within watersheds. The reconstructions document differences in major vegetation composition and disturbance between the burned and unburned watersheds during the past several centuries. Pollen and charcoal stratigraphies from organic sediment accumulations in forested wet depressions indicate that the present experimental design of contrasting disturbance and forest histories has persisted during recent centuries. The unburned watershed has been dominated by spruce (Picea rubens) and fir (Abies balsamea) for 500 years or more and has not recently burned or been substantially cleared. The burned watershed is dominated by a heterogeneous forest of patchy hardwood, mixed wood, and softwood stands. A large portion of this watershed burned severely in 1947 and probably more than once in the 1800s, and has supported heterogeneous successional forests for 200 years or longer. Overall, these results support the underlying premise that the experimental design of this watershed research can be used to infer landscape controls on biogeochemical processes.     

Watershed Nitrogen and Mercury Geochemical Fluxes Integrate Landscape Factors in Long-term Research Watersheds at Acadia National Park, Maine, USA

This paper is an overview of this special issue devoted to watershed research in Acadia National Park (Acadia NP). The papers address components of an integrated research program on two upland watersheds at Acadia NP, USA (44° 20′ N latitude; 68° 15′ E longitude). These watersheds were instrumented in 1998 to provide a long-term foundation for regional ecological and watershed research. The research was initiated as part of EPA/NPS PRIMENet (Park Research and Intensive Monitoring of Ecosystems Network), a system of UV-monitoring stations and long-term watershed research sites located in US national parks. The initial goals at Acadia NP were to address research questions about mercury, acid rain, and nitrogen saturation developed from prior research. The project design was based on natural differences in forests and soils induced by an intense wildfire in one watershed in 1947. There is no evidence of fire in the reference watershed for several hundred years. We are testing hypotheses about controls on surface water chemistry, and bioavailability of contaminants in the contrasting watersheds. The unburned 47-ha Hadlock Brook watershed is 70% spruce-fir mature conifer forest. In contrast, burned 32-ha Cadillac Brook watershed, 4 km northeast of the Hadlock watershed, is 20% regenerating mixed northern hardwoods and 60% shrub/rocky balds. Differences in atmospheric deposition are controlled primarily by forest stand composition and age. The watersheds are gauged and have water chemistry stations at 122 m (Cadillac) and 137 m (Hadlock); watershed maximum elevations are 468 and 380 m, respectively. The stream water chemistry patterns reflect, in part, the legacy of the intense fire, which, in turn, controls differences in forest vegetation and soil characteristics. These factors result in higher nitrogen and mercury flux from the unburned watershed, reflecting differences in atmospheric deposition, contrasting ecosystem pools of nitrogen and mercury, and inferred differences in internal cycling and bioavailabilty.     

Nutrient Export from Watersheds on Mt. Desert Island, Maine, as a Function of Land Use and Fire History

A study of 13 small (less than 7.5 km²) watersheds on Mt. Desert Island, Maine, was conducted from January 1999 to September 2000 to determine nutrient export delivery to coastal waters around the island, and to determine whether a series of wildfires in 1947 have affected nutrient export in burned watersheds. Nutrient export (nitrate–nitrogen, total nitrogen, total phosphorus) was determined for each watershed during the study period, and was normalized by watershed area. The yield of nitrate–nitrogen (N) ranged from 10 to 140 kg/km²/year. Total N yield ranged from 42 to 250 kg/km²/year. Total phosphorus (P) yield ranged from 1.4 to 7.9 kg/km²/year. Watersheds entirely within Acadia National Park (lacking human land-based nutrient sources) exported significantly less total N and total P than watersheds that were partly or entirely outside the park boundary. Nitrate–N export was not significantly different in these two groups of watersheds, perhaps because atmospheric deposition is a dominant source of nitrate in the study area. No relation was observed between burn history and nutrient export. Any effect of burn history may be masked by other landscape-level factors related to nutrient export.     

A Regional Analysis of Lake Acidification Trends for the Northeastern U.S., 1982-1994

Acidic deposition is a regional phenomenon, but its effects have traditionally been studied using site-specific, intensive monitoring. We present trends information for 36 lakes of high-to-moderate acid sensitivity (defined as acid neutralizing capacity [ANC] < 100 eq L-1), and 15 deposition monitoring stations, in the northeastern U.S. for the period 1982-1994. Trends at each site were assessed through use of the Seasonal Kendall tau test; the resulting statistics were combined, through a technique analogous to analysis of variance, to produce quasi-regional estimates of change for key chemical variables. Rates of sulfate deposition declined significantly across all of the northeastern region during this time period, while rates of nitrate and ammonium deposition were unchanged. All lakes exhibited strong decreases in sulfate concentrations in response to declining sulfate deposition, but there was a strong contrast in the response of acid/base status between lakes in New England and lakes in the Adirondacks. As a group, the New England lakes exhibited recovery (ANC = +0.8 eq L-1yr-1, p<0.001), while the Adirondack lakes exhibited either no trend or further acidification (as a group, ANC = -0.5 eq L-1yr-1, p<0.01). This contrast can be attributed to changes in base cation concentrations: New England lakes exhibited base cations declines that were smaller in magnitude than declines in sulfate, producing the observed recovery in ANC; Adirondack lakes showed base cation declines that were very similar to those of sulfate, and no recovery was evident.     

The MAGIC simulation of surface water acidification at, and first year results from, the Bear Brook Watershed Manipulation, Maine, USA

The catchments of East and West Bear Brooks, Maine, USA, have been hydrologically and chemically monitored for 3.5 years. Stream chemistries and hydrographs are similar. These clear water streams are low in ANC (0-70 microeq litre(-1)), with variations caused by changing concentrations of base cations, SO4, NO3 and Cl. The latter range between 90-120, 0-40 and 65-75 microeq litre(-1), respectively. The West Bear catchment is being treated with six applications per year of dry (NH4)2SO4 at 1800 eq ha(-1) year(-1). After one year of treatment, the response of the stream chemistry and the response modelled by MAGIC are similar. Retentions of NH4 and SO4 are nearly 100% and greater than 80%, respectively. The additional flux of SO4 is compensated principally by an increased Ca concentration. Episodes of high discharge in the treated catchment are now characterized by lower ANC and pH, and higher Al than prior to the manipulation. Concentrations of NO3 have increased about 10 microeq litre(-1) during the dormant season, presumably due to additional nitrification of N from NH4. Discharge-chemistry relationships indicate that changes in stream chemistry, except for NO3, are dominated by ion exchange reactions in the upper part of the soil profile.     

Altered Soil-soil Water Interactions Inferred from Stream Water Chemistry at an Artificially Acidified Watershed at Bear Brook Watershed, Maine USA

The Bear Brook Watershed in Maine, USA is the site of a paired watershed study. West Bear (WB) catchment is being artificially acidified with 1,800 eq ha-1 y-1 of (NH4)2SO4. East Bear (EB) serves as the control. After six years of artificial acidification, volume-weighted concentrations in WB, normalized to EB, increased approximately as follows, in eq L-1 : H+, 15; Al (umoles), 50; Al (eq L-1), 100; Ca. 50; Mg. 20; Na, 10; K, 2; SO4, 120; NH4, 2; NO3, 80; HCO3 has decreased 10 eq L-1. Based on changing chemistry, several inferences can be made about soil-soil water interactions.1. Various combinations of cation pairs in stream waters from both catchments are significantly correlated on an annual basis. The strongest linear correlations (r2 typically greater than 0.5), with positive slopes, occur for Mg versus Ca. These relationships suggest soil-soil water equilibria of the type:Ca+2 + Mg-X = Mg+2 + Ca-X; KCa-Mg = ([Mg+2]/[Ca+2])/([Mg-X]/[Ca-X]) or, with assumptions:K'Ca-Mg = [Mg+2]/[Ca+2]The value of K'Ca-Mg remains relatively constant through time in both watersheds, except in WB in and after the fourth year of the manipulation of WB. Thereafter there is preferential depletion (Mg>Ca>na>K), primarily along shallow flow paths - thus altering the solid activity ratios of the exchange surfaces. In EB, base cation concentrations decline with increasing discharge (increasing H+), due to dilution and interaction with soils with lower base saturation. In WB the acidification reverses this relationship, perhaps partly because of displacement of cations by NH4 from the amendments. With progressive depletion of Ca and Mg in the quick-flow paths, concentrations start to decline at higher discharge, in spite of lower pH.2. Sulfate concentrations increased in WB to as high as 230 eq L-1 at high flow. The percentage of added SO4 leached to the stream increased to approximately 65% by the end of 1995. Thus, soils along base-flow paths adsorbed about 35% of the added SO4 in 1995.3. Aluminum concentrations in WB have increased from a pre-manipulation maximum of 10 mole/L at high flow to 60 mole/L. The relationship between Al and H+ is:Al = 0.13(H+)2 + 4.35which could result from either desorption or dissolution of Al to a 2+ specie. This relationship has been relatively constant through the manipulation. The Al/Ca molar ratio increased from pre-manipulation values of 0.1 to 0.3 to 0.8, at higher flow.4. The minimum pH in WB, achieved at highest flow, has decreased from about 5.3 to <4.7, an increase of about 15 eq H+ L-1. The increase in H+ has been approximately 2 eq L-1 yr-1. Neutralization of acidity has been initially accommodated by mobilization of Ca>Mg>Al>Na>K>H; by 1995 the neutralization involves the release of Al>Ca>Mg>NaH>K. Thus, the soils are inferred to (1) have reduced base saturation, (2) preferential proportional loss of mg over Ca, (3) increased SO4 saturation, and (4) higher exchangeable acidity.     

Mass Balances of Mercury and Nitrogen in Burned and Unburned Forested Watersheds at Acadia National Park, Maine, USA

Precipitation and streamwater samples were collected from 16 November 1999 to 17 November 2000 in two watersheds at Acadia National Park, Maine, and analyzed for mercury (Hg) and dissolved inorganic nitrogen (DIN, nitrate plus ammonium). Cadillac Brook watershed burned in a 1947 fire that destroyed vegetation and soil organic matter. We hypothesized that Hg deposition would be higher at Hadlock Brook (the reference watershed, 10.2 μg/m²/year) than Cadillac (9.4 μg/m²/year) because of the greater scavenging efficiency of the softwood vegetation in Hadlock. We also hypothesized the Hg and DIN export from Cadillac Brook would be lower than Hadlock Brook because of elemental volatilization during the fire, along with subsequently lower rates of atmospheric deposition in a watershed with abundant bare soil and bedrock, and regenerating vegetation. Consistent with these hypotheses, Hg export was lower from Cadillac Brook watershed (0.4 μg/m²/year) than from Hadlock Brook watershed (1.3 μg/m²/year). DIN export from Cadillac Brook (11.5 eq/ha/year) was lower than Hadlock Brook (92.5 eq/ha/year). These data show that ∼50 years following a wildfire there was lower atmospheric deposition due to changes in forest species composition, lower soil pools, and greater ecosystem retention for both Hg and DIN.