Chemical Characteristics of Rain Water at an Urban Site of South Western Turkey

In this study, chemical composition of the rain water in Mugla was investigated from February to April 2002. Rain water samples were obtained from Mugla, a small city in south western Turkey. The Yatagan Power Plant is located 30 km northwest of Mugla city. The values of pH and the concentrations of major ions (Ca²⁺, Na⁺, K⁺, SO₄ ²⁻, NO₃ ⁻, NH₄ ⁺) in the rainwater samples were analyzed. The pH varied from 4.5 to 7.7 with an average of 6.9 which was in alkaline range considering 5.6 as the neutral pH of cloud water with atmospheric CO₂ equilibrium. In the total 30 rain events, only two events were observed in acidic range (< 5.6) which occurred after continuous rains. The equivalent concentration of components followed the order: Ca²⁺ > SO₄ ²⁻ > NH₄ ⁺ > NO₃ ⁻ > Na⁺ > K⁺ > H⁺. The volume-weighted mean (VWM) of the measured ionic sum is 371.62 μeq/l. The ratio of between sum cations and sum anions (∑cations /∑ anions) is 1.52 μeq/l. The alkaline components (Ca²⁺, Na⁺, K⁺) contribute 52%, NH₄ ⁺ 8%, whereas, the contribution from the acidic components is relatively small (40%). The low concentrations of H⁺ found in rainwater samples from Mugla suggest that an important portion of H₂SO₄ and HNO₃ have been neutralized by alkaline particles in the atmosphere. The dust-rich local and surrounding limestone environment might have caused the high concentration of Ca²⁺ in Mugla area. The relatively high concentration of NH₄ ⁺ observed at Mugla is suspected to be due to surrounding agricultural. The results obtained in this study are compared with those other studies conducted at various places in the world.     

北京市典型重污染过程中PM2.5载带水溶性无机离子污染特征分析

为研究北京地区冬季PM_(2.5)载带的水溶性无机离子组分污染特征,2013年1月在中国环境科学研究院内采用在线离子色谱(URG-9000B,AIM-IC)对PM_(2.5)中水溶性无机离子(SO_4~(2-)、NO_3~-、Cl~-、NH_4~+、Na~+、K~+、Mg~(2+)、Ca~(2+))进行监测与分析。结果表明,采样期间总水溶性无机离子(TWSI)浓度为61.0μg/m~3,其中二次无机离子SO_4~(2-)、NO_3~-、NH_4~+(SNA)占比达72.3%,在PM_(2.5)中占比为40.29%,表明北京市PM_(2.5)二次污染严重。重污染天[NO_3~-]/[SO_4~(2-)]表明,固定源污染较移动源更为显著。三元相图表明,在空气质量为优的情况下,NH_4~+(在SNA中占比为30.3%~65.5%,下同)主要以NH_4NO_3的形式存在,较少比例以(NH_4)_2SO_4存在;严重污染时,NH_4~+(47.3%~77.9%)主要以(NH_4)_2SO_4形式存在,其次以NH_4NO_3的形式存在,其余的NH_4~+以NH_4Cl的形式存在。[NO_3~-]/[SO_4~(2-)]日变化表明,早、晚机动车高峰影响北京重污染发生。     

Modifications of the transition flow reactor theory for the more accurate measurement of nitric acid and nitrate and ammonium ions

Sixty five samples were taken with a Transition Flow Reactor (TFR) for the measurement of nitric acid (HNO₃) and nitrate particulates (NO ₃ ⁻ ), in a central Athens street having a heavy traffic density, between February 1989 and February 1990. It was established that the TFR theory overestimated HNO₃ and underestimated NO ₃ ⁻ . This is caused by the retention of a fraction of the NO₂ and a fraction of the HNO₂ as NO ₂ ⁻ on the sampler's nylon linear. NO ₂ ⁻ is in turn oxidized to NO ₃ ⁻ and this is determined as HNO₃. Two modifications of the TFR theory are proposed for a better estimation of the HNO₃ and NO ₃ ⁻ . With the first modification HNO₃ is estimated as being equal to the smaller of two values: HNO_{3 TFR} and the value calculated if it is considered that 91% of HNO₃ is retained by the nylon filter. The second modification was based on the quantification of the effect of NO₂ on the concentrations of HNO₃ and NO ₃ ⁻ . This modification is an improvement on the first one and enables the calculation of a lower limit for the concentration of HNO₂. Both modifications improve the accuracy of the TFR sampler in measuring HNO₃ and NO ₃ ⁻ , without altering it structurally. It was also found that the nylon filter partially retains some NH₃, causing a negative error in the measurement of NH ₄ ⁺ with the TFR. The extent of NH₃ retention on the nylon filter is proportional to the HNO₃ concentration. This error must be taken into account whenever NH ₄ ⁺ is being determined.     

Field Survey of Trans-boundary Air Pollution with High Time Resolution at Coastal Sites on the Sea of Japan during Winter in Japan}

An intensive field survey, with 6-h measurement intervals, of concentrations of chemical species in particulate matter and gaseous compounds was carried out at coastal sites on the Sea of Japan during winter. The concentration variation of SO₂(g) and HNO₃(g) were well correlated, whereas the NH₃(g) concentration variation had no correlation with those of SO₂(g) and HNO₃(g). The NH₄ ⁺ (p)/non-sea-salt- (nss-)SO₄ ^{2 −}(p) ratio in particulate matter was mainly affected by the location of the sampling site. One or more concentration peaks of nss-Ca^{2 +} for survey period were observed. Backward trajectories analyses for the highest nss-Ca^{2 +} concentration peaks showed some inconsistency in pathways. We consider that insufficient mixing of the atmosphere and/or insufficient time for the transported air pollutants to react with those discharged locally are the most likely explanations for the discrepancies between the measured products [HNO₃][NH₃] and the calculated values.     

灰霾期间武汉城市区域大气污染物的理化特征

利用湖北省大气复合污染自动监测站2013年的全年监测数据,分析了灰霾期间武汉城市区域大气污染物的理化特征。霾日主要出现在春季、秋季和冬季。霾日与非霾日大气污染物质量浓度和气象参数的对比分析结果显示:高湿度、静风是武汉城市区域霾日的重要气象特征;PM1、PM_(2.5)、PM_(10)、NO_2、CO、NH3的质量浓度,SOR、NOR值以及PM_(2.5)中的二次无机离子(SO2-4、NO-3、NH+4)和部分元素(Pb、Se、Cd、Zn、K)的质量浓度均在霾日明显高于非霾日,而霾日SO2质量浓度仅在冬季略高于非霾日。选取2013年1月的连续灰霾日进行相关性分析,结果表明:污染组分主要来自当地排放(包括直接排放和二次形成),并受当地气象条件影响。此次灰霾过程中PM_(2.5)中的硫酸盐和硝酸盐主要来自气相反应,气态NO_2主要生成了气态HNO_3,而不是HNO_2。     

北京夏季大气主要含氮无机化合物的变化规律与相互作用

利用SJAC-MOBIC/FIA在2006年8月16日—9月9日在线测量了北京城市大气细颗粒物中主要水溶性含氮离子组分(NO₃^-和 NH₄⁺),与重要含氮气态污染物(HNO₃、HNO₂和 NH₃),以追踪细颗粒物中含氮二次无机组分和含氮气态污染物的变化规律及其相互作用。观测期间,NO₃^- 和 NH₄⁺的平均浓度分别为13.08和11.93 μg/m³,它们与SO₄^2-浓度之和在细颗粒物(PM_2.5)中的平均比例为55%,明显高于其他季节;污染过程中,积聚模态颗粒物体积浓度及其与爱根核模态颗粒物体积浓度比值逐渐增加,说明二次转化是北京夏季细颗粒物的重要来源。白天HONO迅速光解产生OH自由基,而OH自由基是生成HNO₃的重要物种,因此HONO和HNO₃具有相反的日变化规律。在温度较高的白天,大气环境不利于NH₄NO₃的生成与存在;夜间低温高湿的条件下硝酸铵理论平衡系数Ke与气态氨和硝酸的乘积Km相当或低于后者,较有利于NH₄NO₃的生成。北京夏季大气具有足量气态NH₃以中和硫酸盐;但在NO₃^-与阳离子的电荷平衡中,金属阳离子也非常重要。     

Atmospheric concentrations of nitric acid, sulfur dioxide, particulate nitrate and particulate sulfate, and estimation of their dry deposition on the urban- and mountain-facing sides of Mt. Gokurakuji, Western Japan

Atmospheric concentrations of nitric acid (HNO₃), sulfur dioxide (SO₂), particulate nitrate and particulate sulfate on the urban- and mountain-facing sides of Mt. Gokurakuji were measured from November 2002 to October 2003, in order to evaluate the effects of anthropogenic activity on air quality and dry deposited nitrate and sulfate on the surfaces of pine foliage. The results showed that HNO₃, SO₂ and concentrations were significantly higher (P < 0.05) on the urban-facing side (1.54, 2.48 and 0.65 μg m⁻³, respectively) than the mountain-facing side (0.67, 1.19 and 0.37 μg m⁻³, respectively), while concentrations did not differ significantly between the two sides (urban-facing: 2.80 μg m⁻³; mountain−facing: 2.05 μg m⁻³). Indirect estimates of dry deposition rates of nitrate and sulfate to the surfaces of pine foliage based on the measured concentrations approximately agreed with the measured values determined by the foliar rinsing technique in a previous study. It was found that HNO₃ was the major source (approximately 80%) of dry deposited nitrate on pine foliage, while the contribution from was about equal to that from SO₂. In conclusion, HNO₃ and SO₂ appear to be dominant species reflecting higher dry deposition rates of nitrate and sulfate on the urban-facing side compared to the mountain-facing side of Mt. Gokurakuji.     

Five-year monitoring study of chemical characteristics of Wet atmospheric precipitation in the southern region of Jordan

Wet atmospheric samples were collected from different locations in the southern region of Jordan during a 5-year period (October 2006 to May 2011). All samples were analyzed for pH, EC, major ions (Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, Cl^?, NO₃ ^?, and SO₄ ^2?), and trace metals (Fe²⁺, Al³⁺,Cu²⁺, Pb²⁺, and Zn²⁺). The highest ion concentrations were observed during the beginning of the rainfall events because large amounts of dust accumulated in the atmosphere during dry periods and were scavenged by rain. The rainwater in the study area is characterized by low salinity and neutral pH. The major ions found in rainwater followed the order of HCO₃?>?Cl^??>?SO₄ ^2? and Ca²⁺?>?Na⁺ > Mg²⁺ > NH₄ ⁺ > K⁺. Trace metals were identified to be of anthropogenic origin resulting from cement and phosphate mining activities located within the investigated area and from heating activities during the cold period of the year (January to April). The wet precipitation chemistry was analyzed using factor component analysis for possible sources of the measured species. Factor analysis (principal component analysis) was used to assess the relationships between the concentrations of the studied ions and their sources. Factor 1 represents the contribution of ions from local anthropogenic activities, factor 2 represents the contribution of ions from natural sources, and factor 3 suggests biomass burning and anthropogenic source. Overall, the results revealed that rainwater chemistry is strongly influenced by local anthropogenic sources rather than natural and marine sources, which is in a good agreement with the results obtained by other studies conducted in similar sites around the world.     

上海青浦地区大气降水的化学特征

利用上海青浦地区2003—2014年观测的大气降水监测资料,分析该区域12 a以来大气降水的酸化程度、化学组成特征,探讨降水中化学成分的不同来源及相对贡献。结果表明:降水pH年均值为4.43~6.33,酸雨频率为2.6%~86.8%,降水酸化程度大致经历了明显恶化和波动变化2个阶段。降水电导率年均值为1.77~4.01 m S/m,呈下降趋势。降水中各离子雨量加权平均当量浓度顺序为SO_4~(2-)NH_4~+Ca~(2+)NO_3~-Cl~-Na~+Mg~(2+)F-K~+,SO_4~(2-)、NH+4、Ca~(2+)和NO_3~-是降水中的主要离子,占离子总量的83.0%;降水类型由硫酸型向硫酸和硝酸混合型转变。降水离子中的二次组分SO_4~(2-)、NO_3~-和NH_4~+绝大部分来源于人为源,Ca~(2+)、Mg~(2+)和K+主要来自于土壤源和人为源的贡献,Cl~-主要来自海洋源,同时人为源的影响也不可忽视。     

Groundwater quality and its suitability for drinking and agricultural use in the Yanqi Basin of Xinjiang Province, Northwest China

The Yanqi Basin in Xinjiang Province is an important agricultural area with a high population density. The extensive agricultural activities in the Yanqi Basin started in the 1950s with flood irrigation techniques. Since then, the groundwater table was raised because of the absence of an efficient drainage system. This obstacle is a crucial factor that restricts sustainable socioeconomic development. Hydrochemical investigations were conducted in the Yanqi Basin, Northwestern China, to determine the chemical composition of groundwater. Sixty groundwater samples were collected from different wells to monitor the water chemistry of various ions. The results of the chemical analysis indicate that the groundwater in the area is generally neutral to slightly alkaline and predominantly contains Na⁺ and Ca²⁺ cations as well as HCO₃ ^? and SO₄ ²⁺ anions. High positive correlations between HCO₃ ^?–Mg²⁺ + Ca²⁺, SO ₄ ^2?–Mg²⁺, SO₄ ^2?–Na⁺ + K⁺, and Cl^?–Na⁺ + K⁺ were obtained. The total dissolved solids (TDS) mainly depend on the concentration of major ions such as HCO₃ ^?, SO₄ ^2?, Cl^?, Ca²⁺, Mg²⁺, and Na⁺ + K⁺. The dominant hydrochemical facies for groundwater are Ca²⁺–Mg²⁺–HCO₃ ^?, Mg²⁺–Ca²⁺–SO₄ ^2?–Cl^?, Na⁺–K⁺–Cl^?–SO₄ ^2?, and Na⁺–K⁺–Mg²⁺–Cl^?–HCO₃ ^? types. The hydrochemical processes are the main factors that determine the water quality of the groundwater system. These processes include silicate mineral weathering, dissolution, ion exchange, and, to a lesser extent, evaporation, which seem to be more pronounced downgradient of the flow system. The saturation index (SI), which is calculated according to the ionic ratio plot, indicates that the gypsum–halite dissolution reactions occur during a certain degree of rock weathering. SI also indicates that evaporation is the dominant factor that determines the major ionic composition in the study area. The assessment results of the water samples using various methods indicate that the groundwater in the study area is generally hard, fresh to brackish, high to very high saline, and low alkaline in nature. The high total hardness and TDS of the groundwater in several places indicate the unsuitability of the groundwater for drinking and irrigation. These areas require particular attention, particularly in the construction of adequate drainage as well as in the introduction of an alternative salt tolerance cropping.     

Acid precipitation-related chemical trends in 18 rivers of atlantic Canada — 1983 to 1992

Using non-parametric techniques, we studied water chemistry changes from 1983 to 1992 in 18 rivers located at the extreme northeastern portion of North America. This period was marked by a decrease in sulfate (SO ₄ ^– ) production in eastern Canada from 1982 to 1986, followed by a levelling off from 1986 to 1992. Nitrate (NO ₃ ^– ) production and deposition generally increased over this whole period. We used two time windows, 1983 to 1989 and 1983 to 1992, to determine if changes in river acidification variables occurred over the ten year period. We found significant trends of increasing pH and acid neutralization capacity (ANC) concentrations at eight sites using both time windows, while SO ₄ ^–2 increased at five and seven sites during the same two time periods. Nitrate concentrations showed few consistent trends, while base cations showed increases in the earlier part of the data set and total organic carbon (TOC) showed long-term decreases. There were few significant trends in hydrogen (H⁺), and a slight decrease in SO ₄ ^–2 exports as opposed to increased concentrations over the same period. We attribute the discrepancy between SO ₄ ^–2 concentration and export trends to be due to evapotranspiration in the basins, causing a concentration of ions in water. Nitrate and calcium exports showed no trends, while TOC decreased at four or five sites, depending on the time window used. Longer data sets tended to produce more detectable trends. Overall, water chemistry in the region is showing the effects of reduced SO ₄ ^– loads and is not yet being affected by the increases in NO ₃ ^– deposition.     

Characteristic Study of Dry Deposition, Concentration, Compositions for Particulates Mass and Ionic Species During Summer and Autumn Season at a Traffic Sampling Site

Aerosol samples for dry deposition and total suspend particulates (TSP) were collected from August to November of 2003 in central Taiwan. Ion chromatography was used to analyze the related water-soluble ionic species (Cl⁻, NO₃ ⁻, SO₄ ²⁻, Na⁺, NH₄ ⁺, K⁺, Mg²⁺ and Ca²⁺). The results obtained in this study indicated that the ambient air particulate mass concentrations in the daytime period (averaged 975.4 μg m⁻³) were higher than the nighttime period (averaged 542.1 μg m⁻³). And the daytime dry deposition fluxes (averaged 58.12 μg m⁻² sec⁻¹) were about 2.2 times as that of nighttime dry deposition fluxes (averaged 26.54 μg m⁻² sec⁻¹) of the downward dry deposition. The average values downward and upward of dry deposition fluxes for the weekend period were almost higher than the weekday period for either daytime or nighttime period. Furthermore, the average daytime dry deposition fluxes (averaged 26.37 μg m⁻² sec⁻¹) were also about 2.3 times as that of nighttime dry deposition fluxes (averaged 11.52 μg m⁻² sec⁻¹). Moreover, the results also indicate that SO₄ ²⁻ and Ca²⁺ have higher average composition for total suspended particulates in the daytime period while Ca²⁺, SO₄ ²⁻, and Na⁺ have the higher average composition for total suspends particulates in the nighttime period.     

Laboratory study of the emission of NO and N2O from some Belgian soils

The NO, NO₂ and N₂O emission was measured, upon application of nitrate, ammonium and both, to four Belgian soils with different characteristics. The addition of NH ₄ ⁺ caused higher NO and N₂O emissions than the addition of no nitrogen, or the addition of NO ₃ ^– . In contrast to the two soils with a pH of approximately 8 the two soils with a pH around 6 showed a considerable delay in production of both NO and N₂O upon the application of the ammonium, probably due to the lag-period of nitrification. The soils with a pH of 8 gave higher emissions on the application of NH ₄ ⁺ than the soils with a pH of 6. The emission of NO₂ was found to be considerably lower than the NO emission from the soils. The NO/NO₂ ratio varied between 5–25 at considerable NO emissions (>50 nmol kg^–1). In the controls of soil 1 and soil 2, which showed very low NO emissions ratios of <1 were observed. The N₂O/NO ratios varied between 5–20 when NO emissions were considerable (>50 nmol kg^–1). Soil 3 and 4 gave lower N₂O/NO ratios than soil 1 and 2. In the controls of soil 1 and soil 2, at low NO emissions, N₂O/NO ratios of >300 were observed. Soil 3 and 4 gave higher NO/NO₂ and lower N₂O/NO ratios than soil 1 and 2.     

Chemistry of fogs at Agra, India: Influence of soil particulates and atmospheric gases

Fog water samples were collected in the months of December and January during 1998–2000 at Agra, India. The samples were analyzed for pH, major anions (F⁻, Cl⁻, SO₄ ²⁻, NO₃ ⁻, HCOO⁻ and CH₃COO⁻), major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺) and NH₄ ⁺ using ion chromatography, ICP-AES and spectrophotometer methods, respectively. pH of fog water samples ranged between 7.0 and 7.6 with a volume weighted mean of 7.2, indicating its alkaline characteristic. NH₄ ⁺ contributed 40%, SO₄ ²⁻ and NO₃ ⁻ accounted for 28%, while Ca²⁺, Mg²⁺, Na⁺ and K⁺ accounted for 16% of the total ionic concentration. The ratios of Mg²⁺/Ca²⁺ and Na⁺/Ca²⁺ in fog water indicates that 50–75% of fog water samples correspond to the respective ratios in local soil. Significant correlation between Ca²⁺, Mg²⁺, Na⁺ and K⁺ suggests their soil origin. The order of neutralization, NH₄ ⁺ (1.4) > Ca²⁺ (0.28) > Mg²⁺ (0.12), indicates that NH₄ ⁺ is the major neutralizing species. Fog water and atmospheric alkalinity were also computed and were found to be 873 and 903 neqm⁻³, respectively. Both of these values are higher than values reported from temperate sites and thus indicate that at the present level of pollutants, there is no risk of acid fog problem. The study also shows that the alkaline nature of fog water is due to dissolution of ammonia gas and partly due to interaction of fog water with soil derived aerosols.     

大同市大气颗粒物浓度与水溶性离子季度分布特征

为研究大同市大气颗粒物质量浓度与水溶性离子组成特征,于2013年2、7、9、12月,分别对大同市及其对照点庞泉沟国家大气背景点进行了PM2.5及PM10的采样,通过超声萃取-IC法测定了样品中的9种水溶性离子,结果表明,大同市大气颗粒物污染1、4季度重于2、3季度,PM2.5季度均值全年均未超标,PM10仅第1季度超标1.4倍,污染状况总体良好,PM2.5与PM10相关系数R为0.75,说明大同市颗粒物污染有较为相近的来源,且不同季节均以粗颗粒物为主;大同市PM2.5中水溶性离子浓度分布为SO2-4、NO-3、NH+4Cl-、Ca2+K+、Na+F-、Mg2+,PM10中Ca2+浓度仅次于SO2-4、NO-3,控制扬尘将有效降低PM10的浓度;PM2.5及PM10中的9种水溶性离子在不同季度的浓度与颗粒物浓度分布规律类似,1、4季度较高,2、3季度较低;由阴阳离子平衡计算结果可知,相关性方程的斜率K为1.045,表明大同市大气颗粒物中阳离子相对亏损,大气细粒子组分偏酸性。NO-3与SO2-4浓度比值均小于1,大同市以硫酸型污染为主,大气中的SO2-4主要来源于人类活动排放。     

Three-year monitoring results of nitrate and ammonium wet deposition in Thailand

Wet deposition is one of the important sources of nitrogen input into the ecosystem. It also contributes to rain acidity in some environments. In this study we reported the annual as well as seasonal trends of nitrogen wet deposition at three locations in Thailand: Bangkok, Chiang Mai and Nan. Comparison of nitrogen wet deposition between in rural and in the urban areas was also made. Daily rainfall was measured and monthly rainwater was collected for nitrogen analysis during 1999–2002. The average NO₃ ^– concentration in rainwater collected from the rural sites (60 km from urban area) was around 0.2–0.3 mg L^–1, while that from the urban areas of Chiang Mai and Nan cities it was 0.4–0.5 mg L^–1. NH₄ ⁺ concentration in rainwater showed the similar ranges to that of NO₃ ^– , except at Nan where concentration was not significantly different between the urban and rural sites. On the other hand, the average concentrations of NO₃ ^– were higher at Bangkok site than other sites, while concentration of NH₄ ⁺ was almost the same between Chiang Mai and Bangkok. Wet deposition of NO₃ ^– at the rural sites of Chiang Mai and Nan ranged from 2.1 to 3.2 kg N ha^–1 yr^–1, while at the urban sites this ranged from about 6 kg N ha^–1 yr^–1 in Chiang Mai and Nan Cities to 8.6 kg N ha^–1 yr^–1 in Bangkok. Wet deposition of NH₄ ⁺ at the rural sites of Chiang Mai and Nan was about 2.4 to 3.6 kg N ha^–1 yr^–1 and at the urban sites of Chiang Mai, Nan and Bangkok this was 7.7, 4.9 and 8.1 kg N ha^–1 yr^–1, respectively. Thus, it was concluded that wet deposition of both nitrogen species was significantly higher at the urban sites than at the rural sites.     

Study on concentration of ambient NH 3 and interactions with some other ambient trace gases

We present diurnal variation of ambient ammonia (NH₃) in relation with other trace gases (O₃, CO, NO, NO₂, and SO₂) and meteorological parameters at an urban site of Delhi during winter period. For the first time, ambient ammonia (NH₃) was monitored very precisely and continuously using ammonia analyzer, which operates on chemiluminescence method. NH₃ estimation efficiency of the chemiluminescence method (>90%) is much higher than the conventional chemical trapping method (reproducibility 4.5%). Ambient NH₃ concentration reaches its maxima (46.17 ppb) at night and minimum during midday. Result reveals that the ambient ammonia (NH₃) concentration is positively correlated with ambient NO (r ²?=?0.79) and NO₂ (r ²?=?0.91) mixing ratio and negatively correlated with ambient temperature (r ²?=???0.32). Wind direction and wind speed indicates that the nearby (~500 m NW) agricultural fields may be major source of ambient NH₃ at the observational site.     

Comparisons of Geochemical Signatures of Biotransformation of Fuel Hydrocarbons in Groundwater

Biotransformation processes play an active role in reducing the environmental impact of fuel hydrocarbon releases to groundwater. Because monitoring data at release locations are typically sparse, spatial variations in geochemical indicator parameters are often called upon as indirect evidence of biotransformation. These parameters include concentrations of electron acceptors (O₂, NO₃ ^-, SO> ₄ ^2- , reduced redox reaction by-products (Fe²⁺, Mn²⁺, CH₄), as well as bicarbonate alkalinity, pH and E_h. However, background variability in a number of these parameters complicates the task of data interpretation, particularly in the case of small data sets. In this study, correlation analyses are applied to geochemical indicator data at six hydrocarbon groundwater contamination sites in California to identify which parameters are the most reliable indicators. The results of the analyses suggest that the most direct indicators of the local redox environment – Fe²⁺, Mn²⁺, CH₄, E_h – yield the most consistent evidence of hydrocarbon biotransformation. Indicators which rely largely on mass balance – O₂, NO ₃ ^- , SO ₄ ^2- , alkalinity – appear to be less reliable. These findings may provide guidance in both the collection and interpretation of groundwater monitoring data at hydrocarbon contamination sites.     

Effects of acid deposition on watershed ecosystems of national parks in the great lakes basin

Legally protected national parks provide an appropriate substrate for essential long-term study of ecosystem structure and function, and for detecting trends in natural and human-induced stress. The absence of unplanned site manipulation in such areas is especially valuable for such research. Our present research has two major components. The first is the long-term ecosystem-level study of the effects of atmospheric contaminants on ecosystem processes. The overall objective is to evaluate ecosystem aquatic/terrestrial linkages and their role in establishing aquatic ecosystem sensitivity to anthropic atmospheric inputs. Four watershed/lake ecosystems, representative of much of the region's diversity, are under study. Two mature boreal sites on Isle Royale are characterized by first-order perennial surface stream input and lake outflow. Two additional mainland northern hardwood sites, one with shallow soils and one with soils derived from glacial till, are characterized by sensitive aquatic systems. One site is in a private reserve and the other in Pictured Rocks National Lakeshore. Surface outflow is gaged by Parshall flume and stage height recorder. Meteorological stations record variables for estimating evapotranspiration. One-tenth ha plots have been established in all watersheds and three sites have had intensive study of precipitation modification by canopy and forest soil. Five-year mean maximum and minimum lake pH varies from 6.85 to 4.94, Ca²⁺ from 1070 to 54 eq l^-1, K⁺ from 5.42 to 8.35 eq l^-1, NH ₄ ⁺ from 10.12 to 3.23 eq l^-1, HCO ₃ ^sup- from 635 to 24 eq l^-1, NO ₃ ^sup- from 3.27 to 1.54 eq l^-1, and SO ₄ ^sup2- from 110 to 52.7 eq l^-1. The relatively high NO ₃ ^sup- values observed in one lake are the result of stream drainage from a watershed dominated by Alnus rugosa, and another has high seasonal NO ₃ ^sup- inputs during spring runoff. However, owing to periodic winter thaws, significant snowpack release of nutrients generally precedes maximum spring stream runoff. Water chemistry in both sensitive and non-sensitive lakes appears to be primarily reflecting how the conterminous terrestrial system is retaining atmospheric inputs more than the quality of direct lake atmospheric input. This is especially evident for H⁺, NO ₃ ^sup- and SO ₄ ^sup2- .The second component is the assessment of watershed acidification, SO ₄ ^sup2- output and soil retention across an input gradient. An anthropic deposition gradient provides the opportunity for intersite time-trend analyses as to the effects of inputs. Our study objective was to see if the decreasing west to east input/output values for SO ₄ ^sup2- , noted in small first-order watersheds in national parks from Minnesota to Ohio, might be related to present atmospheric inputs, potential and total soil SO ₄ ^sup2- adsorption, or soil SO ₄ ^sup2- desorption from earlier higher inputs. Precipitation pH ranged from 5.05 at Fernberg, Minnesota to 4.24 at Wooster, Ohio. Minimum and maximum concentrations of NH ₄ ⁺ , NO ₃ ^sup- , SO ₄ ^sup2- and Cl^- were also found at these stations. Stream water concentrations of NO ₃ ^sup- and SO ₄ ^sup2- increase in a similar but sharper gradient. Streams are well buffered. Cation, HCO ₃ ^sup- , NO ₃ ^sup- and especially SO ₄ ^sup2- output increase west to east, but H⁺ output decreases. At the eastern site stream SO ₄ ^sup2- concentration and output exceed HCO ₃ ^sup- . Potential soil SO ₄ ^sup2- adsorption capacity increases eastward, but this capacity is filled. Crystalline Fe hydrous oxides appear more effective than amorphous Fe hydrous oxides at adsorbing SO ₄ ^sup2- . High anthropic anion inputs, inability of forest soil to adsorb additional inputs and perhaps SO ₄ ^sup2- desorption appear responsible for the replacement of HCO ₃ ^sup- by SO ₄ ^sup2- in stream water. The major cation accompanying SO ₄ ^sup2- is Ca²⁺.Contribution from Fourth World Wilderness Congress—Acid Rain Symposium, Denver (Estes Park), Colorado, September 11–18, 1987.     

Deposition in boreal forests in relation to type, size, number and placement of collectors

Open precipitation and throughfall was collected at a Norway spruce stand in Finland using funnel-type collectors and at a black spruce stand in Canada using trough-type collectors. The presence or absence of a rim on the funnel, funnel diameter (9, 14 and 20 cm) and length of sampling period (1, 2 and 4 weeks) on monthly values were evaluated at the Norway spruce stand, and the number of collectors required for defined levels of accuracy and precision of throughfall loads to be reached and the influence of the spatial arrangement of collectors on solute concentrations was studied at both stands. The presence of a rim had no significant effect on open precipitation and throughfall amounts, but did on throughfall DOC, Ca²⁺, Mg²⁺, K⁺, Na⁺ and Cl⁻ ion loads. Deposition loads increased with decreasing funnel diameter; for open precipitation, this was due to increased catch efficiency while for throughfall the increase was attributed to canopy interaction and leaching of litter trapped in the collectors. Calculated monthly H⁺ loads decreased and those for all other constituents increased with collection period length. Using 15 collectors at the Norway spruce stand would allow throughfall loads to be determined to within 20% of the true mean weekly value with a confidence level of 95% for most solute, but not for NH₄ ⁺–N, NO₃ ⁻–N, Mg²⁺ and SO₄ ²⁻-S. Using 15 trough collectors, the same confidence level at the more heterogeneous black spruce stand would only be achieved for H⁺, Cl⁻, DOC and SO₄ ²⁻-S loads. In both stands, using either random or systematic placements of throughfall collectors gave similar results.