全自动甲基汞分析仪测定水和废水中甲基汞

建立了全自动甲基汞分析仪测定水和废水中甲基汞的方法,对较清洁的地表水和一般废水样品可直接衍生化测定,对基体复杂水样则需蒸馏后再衍生化测定。该法在水样中甲基汞含量为0~1 000 pg范围内线性良好,相关系数r为0.999 7,检出限为0.002 ng/L,标准参考物质测定结果均在参考值范围内,相对标准偏差为1.1%,加标回收率为83.2%~96.6%。该法适用于水及废水中甲基汞的检测。     

Mercury Contamination of Biota from Acadia National Park, Maine: A Review

We reviewed literature reporting both total and methylmercury from biota from Acadia National Park, Maine, USA. Our review of existing data indicates that 1) mercury contamination is widespread throughout the Park’s various aquatic ecosystems; 2) mercury pollution likely represents a moderate to high risk to biota inhabiting the Park; and 3) biota at all trophic levels possess elevated concentrations of both total and methylmercury. Watershed fire history and the resulting post-fire forest succession patterns are an important landscape attribute governing mercury cycling at Acadia National Park. Therefore, park service personnel should consider these factors when planning and implementing Hg biomonitoring efforts. Additional baseline funding from the National Park Service for Hg research and biomonitoring will likely be required in order to further evaluate the spatial and temporal patterns of mercury contamination in the park’s biota. An erratum to this article can be found at     

测定水中铁、锰、汞时前处理问题探讨

基于大量实测数据统计,比较了测定水中铁、锰、汞3种重金属时,样品是否过滤、加酸保存等前处理方式对测定结果的影响,提出铁、锰水样需过滤检测,汞水样不能过滤检测,且3种金属的水样均需加酸保存,这样测定的结果才能根据现行水环境质量标准进行评价。     

高效液相色谱-电感耦合等离子体质谱联用测水中有机汞

建立了高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定水样中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。采用醋酸铵-L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,Agilent Zorbax Plus C18柱分离,经前处理的水样在液相色谱中分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞、苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈良好的线性关系,线性相关系数均大于0.999 5。仪器检出限为0.09~0.12μg/L,方法检出限为0.4×10-6~0.6×10-6mg/L,3种有机汞样品加标的RSD均小于11.3%,2个水平的加标回收率为74.4%~83.2%。     

Aldehyde Concentrations in Ambient Air of Coastal Georgia, U.S.A.

Aldehydes are an airborne byproduct of many industrialprocesses, vehicle transportation, and emissions fromnumerous natural sources. To characterize aldehydeconcentrations in ambient air of the Savannah, Georgiaarea, air samples for 3 aldehydes (formaldehyde,acetaldehyde, and propionaldehyde) were collected atfive sites on a monthly basis over a 12-month periodfrom December of 1995 through November 1996. Four ofthe sites were in central Savannah and the fifth sitewas located in a rural area about 56 km south ofSavannah. During each 24-hr sampling episode, sampleswere collected in two 12-hr periods approximatingdaylight and nighttime hours, following U.S. EPAMethod TO-11. Formaldehyde concentrations ranged from0.17 to 6.80 g m^-3, acetaldehydeconcentrations ranged from 0.07 to7.60 g m^-3, and propionaldehyde levels rangedfrom 0.02 to 9.10 g m^-3. On average, thefour sites in Savannah had higher aldehydeconcentrations than the rural site (2.0 versus1.2 g m^-3 for formaldehyde, 2.3 versus1.7 g m^-3 for acetaldehyde, and 1.2 versus1.0 g m^-3 for propionaldehyde). The daytimeconcentrations for formaldehyde and acetaldehyde werehigher than the nighttime levels. The data from allthe sites were within published worldwide backgroundvalues for aldehydes.     

Controls on Mercury and Methylmercury Deposition for Two Watersheds in Acadia National Park, Maine

Throughfall and bulk precipitation samples were collected for two watersheds at Acadia National Park, Maine, from 3 May to 16 November 2000, to determine which landscape factors affected mercury (Hg) deposition. One of these watersheds, Cadillac Brook, burned in 1947, providing a natural experimental design to study the effects of forest type on deposition to forested watersheds. Sites that face southwest received the highest Hg deposition, which may be due to the interception of cross-continental movement of contaminated air masses. Sites covered with softwood vegetation also received higher Hg deposition than other vegetation types because of the higher scavenging efficiency of the canopy structure. Methyl mercury (MeHg) deposition was not affected by these factors. Hg deposition, as bulk precipitation and throughfall was lower in Cadillac Brook watershed (burned) than in Hadlock Brook watershed (unburned) because of vegetation type and watershed aspect. Hg and MeHg inputs were weighted by season and vegetation type because these two factors had the most influence on deposition. Hg volatilization was not determined. The total Hg deposition via throughfall and bulk precipitation was 9.4 μg/m²/year in Cadillac Brook watershed and 10.2 μg/m²/year in Hadlock Brook watershed. The total MeHg deposition via throughfall and bulk precipitation was 0.05 μg/m²/year in Cadillac Brook watershed and 0.10 μg/m²/year in Hadlock Brook watershed.     

Response of Mercury Contamination in Fish to Decreased Aqueous Concentrations and Loading of Inorganic Mercury in a Small Stream

Approximately 250 000 kg of mercury was lost towater and soils at the U.S. Dept. of Energy Y-12 Plantin Oak Ridge, Tennessee in the 1950s and early 1960s. A creek originating within the plant receivedcontinuous inputs of waterborne mercury, predominantlyas dissolved inorganic mercury, from groundwater,streambed contamination, and sump and process waterdischarges to the contaminated storm sewer network.These produce aqueous total mercury concentrations of1–2 g L^-1 in the upper reaches of the stream,decreasing to about 0.1–0.2 g L^-1 in its lowerreaches. A program to reduce mercury concentrationsin the creek identified specific sources (buildingsumps, contaminated springwater seeps, foundationdrains, and contaminated piping) and rerouted wateraround contaminated portions of the drain system orcollected and treated mercury-contaminated waterbefore discharging it. As a result, waterbornemercury concentrations in the creek and total mercuryloading were reduced from 1.8 g L^-1 to0.6 g L^-1 and 100 to 20 g d^-1, respectively, in the last 5 yr.Mean mercury concentrations in fish nearest sourceareas in the creek headwaters decreased at roughly thesame rate as waterborne total mercury concentrationsover the past five years, but at the facility boundarydownstream the decline in mercury bioaccumulation wasmuch less. At sites 5–15 km farther downstream, nodecrease was evident. Dissolved methylmercury tendedto increase with distance downstream in a patterninverse to that noted for its dissolved inorganicmercury precursor.Improvements in water quality and modification ofweirs to allow the passage of fish have resulted inthe establishment of large populations of fish inmercury-contaminated headwater areas previously devoidof fish. It may be that the accumulation, retention,and eventual downstream transport of this reservoir ofbiologically incorporated methylmercury has acted tobuffer against expected reductions in mercury in fishat downstream sites.     

Mercury, Methylmercury, and Selenium Concentrations in Eggs of Common Loons (Gavia immer) from Canada

Concentrations of Hg and Se were determined for a total of 125Common Loon (Gavia immer) eggs collected from lakes in Alberta, Saskatchewan, Ontario, Quebec, New Brunswick and NovaScotia, Canada between 1972 and 1997. Resulting data were compared to Hg and/or Se concentrations known or suspected tocause reproductive impairment in birds. Organic (methyl) Hg analyses were also performed on a subset of 24 loon eggs. Thirty-nine of 125 eggs had total Hg levels exceeding those (0.6 g g^-1 ww, or 2.5 g g^-1 dw)previously reported to be associated with reproductive impairment in common loons (Barr, 1986), and 9 of 125 eggshad Hg concentrations higher than the level associated withreproductive impairment in birds generally 1 g g^-1 ww; (Thompson, 1996). Selenium concentrations in loon egg samples were less than levels known to cause reproductiveimpairment in birds. A weak but significant positive correlation was observed between egg-Hg and -Se concentrations(r = 0.511, p < 0.05). On average, methylmercury accounted for about 87% of total Hg in 24 eggs analysed for both total and organic Hg. In this subset of eggs, the relationship between organic (methyl) Hg and Se was significant (r = 0.538, p = 0.007) while that found between inorganic Hg and Se in the same eggs was not significant (r = 0.353, p = 0.091). This relationship was unexpected and was contrary to relationships established for organic and inorganic Hg vs. Se in adult loon liver and kidney tissue (Scheuhammer et al., 1998b).     

氯磺酚偶氮硫代若丹宁光度法测定环境水样中的汞

研究了氯磺酚偶氮硫代若丹宁(HSCT)与汞的显色反应。在pH3 8的HAc-NaAc缓冲介质中,TritonX-100存在下,HSCT与汞反应生成2∶1稳定络合物,λmax=550nm,体系ε=8 46×104L·mol-1·cm-1。汞含量在0—1 5mg/L内符合比耳定律。方法可用于水样中痕量汞含量的测定。     

株洲夏季大气中气态总汞浓度特征

为研究株洲市夏季优良天气下大气中气态总汞(TGM)的浓度特征,于2013年8月利用大气汞分析仪(2537X,加拿大)进行了20 d的连续在线观测。结果显示,实验期间株洲市大气TGM的平均浓度为(4.20±3.37)ng/m3,中值浓度为3.40 ng/m3,高于背景地区和沿海城市,略低于国内其他重点城市。晴天、阴雨天TGM浓度分别为3.59、7.96 ng/m3。晴天TGM浓度具有一定日变化规律,最高值出现在早上7:00~9:00,之后逐渐降低,17:00出现最低值;TGM白天和夜间浓度分别为3.57、3.62 ng/m3,昼夜变化不大。晴天TGM与一次污染物SO2、CO、NO2具有显著的正相关性,与O3呈显著负相关性。株洲市夏季主导风向为东南风,该方向没有明显污染源,西北方向风向频率较低,但TGM浓度明显升高,其主要来源可能是位于西北方向的清水塘工业区。     

Mercury Concentrations in Fish from Lake Meredith, Texas: Implications for the Issuance of Fish Consumption Advisories

We examined how length of fish is related to mercury concentrations in muscle tissue of seven species of fish from Lake Meredith, Texas and determined how sex and growth rate are related to mercury concentration in walleye (Sander vitreus). Flathead catfish (Pylodictis olivaris), walleye and white bass (Morone chrysops) had the highest concentrations of mercury and channel catfish (Ictalurus punctatus), common carp (Cyprinus carpio), river carpsucker (Carpiodes carpio) and gizzard shad (Dorosoma cepedianum) had the lowest concentrations of mercury. Mercury concentrations were positively correlated with total length (TL) of fish for all species except gizzard shad, which exhibited a negative correlation between mercury concentration and TL. Male walleye grew more slowly than females, and males had higher concentrations of mercury than females. We also assessed the differences in fish consumption advisories that would be issued using Texas Department of State Health Services (DSHS) guidelines versus United States Environmental Protection Agency (USEPA) recommendations. Using DSHS guidelines, no fish species in Lake Meredith would be issued a fish consumption advisory. Nevertheless, DSHS has issued an advisory for walleye in Lake Meredith, possibly due to an inadequate sample size of fish. Using USEPA guidelines, a fish consumption advisory would be issued for the largest size class of flathead catfish but no advisory exists for flathead catfish in Lake Meredith. We suggest that when fish in a lake may be contaminated with mercury, all game fish in the lake should be assessed, and mercury advisories should take fish size into account.     

Restoration of the Kissimmee River, Florida: Water Quality Impacts from Canal Backfilling

The planned restoration of the Kissimmee River ecocystem will backfill approximately 35 km of flood control canal (C-38) that cuts through the meandering river channel, re-establish natural flow patterns, and restore the river/floodplain ecosystem. Water quality monitoring, including nutrients, total suspended solids (TSS), turbidity, dissolved oxygen (DO), and mercury, was conducted during a pilot `test fill' project to determine if soil disturbance during canal backfilling would negatively impact these water quality constituents. Surface water nutrient concentrations varied little between sites. Generally, highest concentrations occurred prior to construction, with lowest concentrations occurring during and after construction. During construction, TSS concentrations increased at sites immediately upstream, downstream, and adjacent to the construction area. Increased turbidity was generally restricted to areas immediately upstream and downstream of the test plug, with maximum levels occurring during the initial construction phase. Some downstream increases in turbidity were observed; however, impacts were short-term, lasting less than 24 h. Depresssed DO levels (<2 mg/l) were observed upstream of the test plug following completion of the initial plug across C-38. Dissolved oxygen levels remained low for approximately 6 weeks, with no apparent ecological impacts. Total mercury (HgT) within canal sediment ranged from 9.2–180 ng/g and methylmercury concentrations ranged from 0.037–0.708 ng/g. Concentration of total mercury and total methylmercury (MeHgT) in the backfill material were much lower than concentrations in the canal sediment. No significant change in aqueous HgT concentrations occurred over the sampling period, although construction-induced turbidity could have temporarily caused a slightly elevated concentration immediately downstream of the construction site. Methylmercury concentrations in the water column ranged from 0.033–0.518 ng/l. No significant differences in mean MeHgT concentrations occured between sites or between sampling dates, except at one downstream site where MeHgT declined significantly over the sampling period.     

Sources and Concentrations of Mercury and Selenium In Compartments within the Las Vegas Wash During A Period of Rapid Change

The Las VegasWash, which drains the Las Vegas valley watershed and provides the second largest inflow to Lake Mead, is being dramatically altered with erosion control structures and wetland restoration efforts. The impact of these changes on the cycling and distribution of Hg and Se is of particular interest because of their tendency to bioaccumulate and because of a lack of information on these contaminants in the Wash. In this study, we determined concentrations of Hg and Se in surface water (monthly), groundwater (once) and sediments (quarterly) from strategic locations within and along theWash during 2002 and 2003. The data was used to characterize Se sources and loading into theWash. Samples containing resurfacing groundwater and urban runoff (LW10.75 and Duck Creek) had significantly higher yearly means (13.7 ± 4.4 and 23.8 ± 4.1μg/L, respectively) compared with mainstream samples containing primarily treated wastewater (2.8 ± 0.8μg/L). Investigation of Se in tributaries, street runoff and rain suggest that the source of the elevated Se is likely groundwater seeps located within a relatively narrow geographic band on the southeast side of the valley. Se content of sediments was similar, except for LW10.75 which was rich in organic matter. Hg concentrations in the water and sediments were low, averaging 4±5 ng/L and 34±20 ng/g, dw, respectively. Overall, this study suggests that water quality remains relatively stable despite changes in theWash and managers of developing wetlands should not use tributary water as source water.     

提高环境水中纳克级超痕量汞测定灵敏度的研究

对ｎｇ／Ｌ级超痕量汞测定中的消解、测定各步骤对灵敏度的影响进行了研究。得出结论：采用高纯氩气作载、屏气,选择高负压值和高扩展倍率能明显提高灵敏度;选择合适的消解时间和缩短测定时间能使灵敏度略有提高;试剂和玻璃器皿所带给空白的痕量汞对提高灵敏度不利,应作除汞处理。     

Biomagnification factors (fish to Osprey eggs from Willamette River,Oregon, U.S.A.) for PCDDs,PCDFs, PCBs and OC pesticides

A migratory population of 78 pairs of Osprey (Pandion haliaetus) nesting along the Willamette River in westernOregon was studied in 1993. The study was designed to determinecontaminant concentrations in eggs, contaminant concentrationsin fish species predominant in the Ospreys diet, andBiomagnification Factors (BMFs) of contaminants from fish specieseaten to Osprey eggs. Ten Osprey eggs and 25 composite samplesof fish (3 species) were used to evaluate organochlorine (OC)pesticides, polychlorinated biphenyls (PCBs), polychlorinateddibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans(PCDFs). Mercury was also analyzed in fish. Geometric meanresidues in Osprey eggs were judged low, e.g., DDE 2.3 g g^-1 wet weight (ww), PCBs 0.69 g g^-1, 2,3,7,8-TCDD 2.3 ng kg^-1, and generally well below known threshold values for adverse effects on productivity, and the population was increasing. Osprey egg residue data presentedby River Mile (RM) are discussed, e.g., higher PCDDs were generally found immediately downstream of paper mills and eggsfrom the Willamette River had significantly elevated PCBs and PCDDs compared to reference eggs collected nearby in the CascadeMountains. Prey remains at nest sites indicated that the Largescale Sucker (Catostomus macrocheilus) and NorthernPikeminnow (Ptychocheilus oregonensis) accounted for an estimated 90.1% of the biomass in the Osprey diet, and composite samples of these two species were collected from different sampling sites throughout the study area for contaminant analyses. With the large percentage of the fishbiomass in the Osprey diet sampled for contaminants (and fisheaten by Ospreys similar in size to those chemically analyzed),and fish contaminant concentrations weighted by biomass intake, a mean BMF was estimated from fish to Osprey eggs for the largeseries of contaminants. BMFs ranged from no biomagnification(0.42) for 2,3,7,8-TCDF to 174 for OCDD. Our findings for themigratory Osprey were compared to BMFs for the resident HerringGull (Larus argentatus), and differences are discussed. Webelieve a BMF approach provides some basic understanding ofrelationships between contaminant burdens in prey species offish-eating birds and contaminants incorporated into their eggs,and may prove useful in understanding sources of contaminants inmigratory species although additional studies are needed.     

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.     

高效液相色谱-氢化物发生-原子荧光光谱联用技术测定水中烷基汞

建立了高效液相色谱(HPLC)-氢化物发生(HG)-原子荧光光谱(AFS)联用技术分析地表水及废水中甲基汞和乙基汞的方法。样品经二氯甲烷萃取,再以半胱氨酸+乙酸铵溶液反萃取富集,并进入高效液相色谱分离,经形态分析预处理装置后,借助原子荧光光谱法检测。在优化分离条件下,甲基汞和乙基汞在1～50μg/L范围内呈现良好的线性关系,对于标准水样、地表水和废水实际水样,加标平均回收率均为80%～110%。平行进样7次1μg/L的汞混合标准溶液,甲基汞和乙基汞的色谱峰面积的相对标准偏差分别为5.2%和3.9%,检出限则分别为0.4 ng/L和0.7 ng/L。该检测方法前处理简单、回收率稳定、灵敏度和准确度高、检出限低、杂质干扰少、监测费用低,便于在普通实验室推广和应用。     

黑龙江流域水环境背景值研究进展

黑龙江流域地处世界三大黑土区之一的中国东北平原,土壤腐殖质含量高,这些腐殖质随着地面径流进入水体,成为流域溶解性有机物(DOM)的自然本底(环境背景)。自然本底的存在导致流域水质有机污染综合指标不能真实反映流域的人为污染,流域背景区内高锰酸盐指数、化学需氧量背景值范围分别为3.0～11.7、14.3～40.5 mg/L。流域部分水质考核断面水质受到有机质背景值的影响。由于叠加人为污染,定量分析高锰酸盐指数、化学需氧量背景值范围存在很大难度。重金属元素相对稳定,相对于"六五"时期重金属背景值,目前水体中重金属含量普遍升高。结合水环境管理需求,背景值研究成果应用于水环境管理还需要进一步深入研究和实践。笔者在综述黑龙江流域水环境背景值研究基础上,总结目前存在的问题,提出水环境背景值研究建议,为科学客观评价流域水质提供参考。     

Impervious Surface Area as a Predictor of the Effects of Urbanization on Stream Insect Communities in Maine, U.S.A.

The influence of urbanization on stream insect communities was determined by comparing physical, chemical, and biological characteristics of streams draining 20 catchments with varyinglevels of urban land-cover in Maine (U.S.A). Percent total impervious surface area (PTIA), which was used to quantify urbanland-use, ranged from 1–31% among the study catchments.Taxonomic richness of stream insect communities showed an abruptdecline as PTIA increased above 6%. Streams draining catchmentswith PTIA < 6% had the highest levels of both total insect and EPT (Ephemeroptera + Plecoptera + Trichoptera) taxonomic richness. These streams contained insect communities with a totalrichness averaging 33 taxa in fall and 31 taxa in spring; EPT richness ranged from an average of 15 taxa in fall and 13 taxa inspring. In contrast, none of the streams draining catchments with6–27% PTIA had a total richness > 18 taxa or an EPT richness> 6 taxa. Insect communities in streams with PTIA > 6% were characterized by the absence of pollution-intolerant taxa. The distribution of more pollution-tolerant taxa (e.g.Acerpenna (Ephemeroptera); Paracapnia, Allocapnia (Plecoptera); Optioservus, Stenelmis (Coleoptera); Hydropsyche, Cheumatopsyche (Trichoptera)), however, showed little relation to PTIA. In contrast to the apparent threshold relationship between PTIA and insect taxonomic richness, both habitat qualityand water quality tended to decline as linear functions of PTIA.Our results indicate that, in Maine, an abrupt change in stream insect community structure occurs at a PTIA above a threshold ofapproximately 6% of total catchment area. The measurement of PTIA may provide a valuable tool for predicting thresholds for adverse effects of urbanization on the health of headwater streams in Maine.     

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.