The Precision of Precipitation Chemistry Measurements in the Canadian Air and Precipitation Monitoring Network (CAPMoN)

Precision estimates are presented for precipitation chemistry and depth measurements made by the Canadian Air and Precipitation Monitoring Network (CAPMoN). The estimates were made for daily measurements of ion concentration and precipitation depth as well as for weekly, 28-day, seasonal and annual precipitation-weighted mean concentrations and depths. The data on which the estimates are based were collected from collocated samplers at five CAPMoN sites during the period 1985 to 1993. The data pairs from the collocated samplers were used to calculate the between-instrument error defined as 1/2 times the difference between the paired sample concentrations (or depths). For all of the ion concentrations and depths, the between-sampler errors were found not to be normally distributed, but the normality of the distributions improved with the length of the (volume-weighting) time period considered. A set of quantitative measures of overall network precision were derived in absolute (mg L^-1) and relative (%) units. These included the Modified Median Absolute Deviation (M.MAD), the P90% probability values and the Coefficient of Variation (CoV). The latter, defined as the percent ratio of the M.MAD to the median concentration (or depth), represents the relative precision at the center of the error and concentration (and depth) distributions. Based on the CoV values, the relative precision of the CAPMoN measurements was very high (better than 4%) for SO ₄ ^2- , NO ₃ ^- , pH, H⁺, NH ₄ ⁺ , sample depth and standard gauge depth, and not as high (between 10 and <35%) for Cl^-, Na⁺, Ca²⁺, Mg²⁺, and K⁺. The ions with the lowest median concentrations had the poorest relative precision since so many of the concentrations were at or near the analytical detection limit. Except for the sample and standard gauge depths, both the absolute and relative precision improved with the length of the precipitation-weighting period. Detailed statistical testing established that the precision of the daily measurements is dependent on a number of factors, the most dominant being sample depth and concentration, i.e., the absolute precision improves with increasing sample depth and decreasing concentration. The strength of these relationships diminished with the length of the precipitation-weighting period being considered. Laboratory-related sources of imprecision were found to account for less than 4% of the overall daily measurement imprecision for most species, while field-related sources of imprecision accounted for the balance. Specialized plots are shown which allow data users to estimate the absolute and relative precision at any concentration and depth value.     

A Comparison of the Precipitation Chemistry Measurements Obtained by the CAPMoN and NADP/NTN Networks

Precipitation chemistry measurementsobtained by the Canadian Air and PrecipitationMonitoring Network (CAPMoN) and the U.S. NationalAtmospheric Deposition Program/National Trends Network(NADP/NTN) have been examined using more than 7 yrof collocated data from two sites, namely, Sutton,Quebec, Canada and State College, Pennsylvania, U.S.A.In the case of the CAPMoN data, weeklyprecipitation-weighted mean concentrations, totalsample depths and total standard gauge depths werecomputed from daily data and compared to thecorresponding weekly sampling data of the NADP/NTNnetwork. Seasonal and annual precipitation-weightedmean concentrations and deposition values were alsocomputed for both networks and compared. Statisticallysignificant between-network biases were found to existin the weekly results for most of the measuredvariables, particularly standard gauge depth, sampledepth, pH, H⁺, NO₃^-,NH₄⁺,Na⁺; the NADP/NTN values were consistently lowerthan those of CAPMoN with the exception of pH andNa⁺. The magnitude of the biases was less than35% of the median CAPMoN weekly value for the 7 yr. For most of the measured parameters, thevariability of the between-network differencesrepresented less than 20% of the median CAPMoN weeklyvalue. Both the between-network biases andvariabilities were functions of several physicalparameters, the most dominant being the sample depthand the ionic concentration. For seasonal and annualdeposition values, statistically significantbetween-network biases were found for H⁺,SO₄^2-, NO₃^-,Ca²⁺,NH₄⁺ for both periods; for Mg²⁺ andK⁺ for seasonal data; and Cl^- for yearlydata, with the NADP/NTN deposition values being lowerthan those of CAPMoN. The relative biases ranged from7 to 37%. Part of the between-network bias in thedeposition estimates was directly attributable to astrong bias in the standard gauge depths of the two networks.     

Analysis of Wet Precipitation of Air Pollutants in Mumbai (India)

Bulk precipitation samples at Mumbai (India) were collectedduring the monsoon seasons of 1991 to 1996 and analysed forionic concentrations using an Ion Chromatograph DIONEX model100. The variability of sulphate to nitrate ratio in rainwaterfluctuates in a wide range from 1.5 to 20 and governed by thesulphate concentrations in the sample. The regression analysisof the data reveals that in the bulk precipitation at Mumbai, SO₄^2- is becoming increasingly important relative toNO₃^-. The role of meteorological influences onscavenging of air pollutants by rain water has been tried toexplain the phenomena. The computed wet deposition rates for Sand N during 1991–1996 show that the S deposition is higherthan N in all the years. There is a wide fluctuation indeposition rates of S ranging from 2 to 55 kg km² per annum.     

博乐市降水酸度特征初探

根据博乐市2005—2010年降水数据,对酸雨发生的原因进行了分析。分析结果表明：博乐市地形适合水汽输入,存在远距离污染物跨境传输和产生连续大降雨的条件,使其境内产生酸雨的可能性加大;酸雨发生在冬季采暖期,且NO3^-浓度比未发生酸雨时略高;另外,博乐市属北方干旱区城市,土壤偏碱性,降水总体为偏弱碱性特点不变。除以上主...     

奎屯市大气降水现状分析及评价

为了解奎屯市大气降水状况及主要污染物,奎屯市监测站于2002年对大气降水进行了为期一年的酸雨监测。本文根据监测结果,介绍了奎屯市酸雨现状,对其成因进行了分析,并提出防治酸雨污染的可行性建议。     

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.     

新疆大气氮沉降监测研究进展浅析

通过对新疆12个监测点氮沉降研究结果发现,无机活性氮浓度(pNH4+、pNO3-、NH3、NO2)在不同生态系统存在较大的时空差异,氮沉降通量变化随人为干扰程度呈递增趋势.总结了当前新疆大气氮沉降监测研究进展,包括主要监测方法、不同生态系统大气氮素干沉降的时空差异性分析、大气氮素干湿沉降通量估算.对大气氮素干湿沉降通量...     

Precipitation Chemistry and Occurrence of Acid Rain Over Dhanbad, Coal City of India

The present study investigated the chemical composition of wet atmospheric precipitation over Dhanbad, coal city of India. The precipitation samples were collected on event basis for three years (July 2003 to October 2005) at Central Mining Research Institute. The precipitation samples were analyzed for pH, conductivity, major anions (F, Cl, NO₃, SO₄) and cations (Ca, Mg, Na, K, NH₄). The pH value varied from 4.01 to 6.92 (avg. 5.37) indicating acidic to alkaline nature of rainwater. The pH of the rainwater was found well above the reference pH (5.6), showing alkalinity during the non-monsoon and early phase of monsoon, but during the late phase of monsoon, pH tendency was towards acidity (<5.6~pH) indicating the non-availability of proper neutralizer for acidic ions. The observed acidic events at this site were 91, (n = 162) accounting 56% for the entire monitoring months. The (NO₃ + Cl)/SO₄ ratio in majority of samples was found below 1.0, indicating that the acidity is greatly influenced by SO₄. The calculated ratio of (Ca + NH₄)/(NO₃ + SO₄) ranges between 0.42–5.13 (average 1.14), however in most of the samples, the ratio is greater than unity (>1.0) indicating that Ca and NH₄ play an important role in neutralization of acidic ions in rainwater. Ca and SO₄ dominate the bulk ionic deposition and these two ions along with NH₄ accounts 63% of the annual ionic deposition.     

乌鲁木齐市大气降水的化学特征分析

讨论了乌鲁木齐市2004年1～12月年度降水的酸碱性、离子组分变化规律与特征,阐述了乌鲁木齐市城市降水的基本现状,分析了降水的变化规律,对主要成因进行了初步探讨,指出乌鲁木齐市的硫酸型降水污染应该从总量上控制SO2。并从源头上削减SO2的排放量。     

Estimation of Critical Loads of Acidity for Lakes in Northeastern United States and Eastern Canada

The New England Governors and Eastern Canadian Premiers (NEG/ECP) adopted the Acid Rain Action Plan in June 1998, and issued a series of action items to support its work toward a reduction of sulfur dioxide (SO₂) and nitrogen oxide (NO_x) emissions in northeastern North America. One of these action items was the preparation of an updated critical load map using data from lakes in the NEG/ECP area. Critical load maps provide a more complete index of the surface water sensitivity to acidification. Combined sulfur and nitrogen critical loads and deposition exceedances were computed using Henriksen's Steady-State Water Chemistry (SSWC) model. Results show that 28% of all 2053 lakes studied have a critical load of 20 kg/ha/year or less, making them vulnerable to acid deposition. Emission reductions, and more specifically SO₂ emission reductions have proven beneficial because critical loads were exceeded in 2002 for 12.3% of all studied lakes. Those lakes are located in the more sensitive areas where geology is carbonate-poor. Of these lakes, 2.9% will never recover even with a complete removal of SO₄ deposition. Recovery from acidification for the remaining 9.4% of the lakes will require additional emission SO₂ reductions.     

Assessment of Treatment Alternatives for Laboratory COD Wastewater: a Practical Comparison with Emphasis on Cost and Performance

This study focused on investigation of treatment alternativesfor COD wastewater from academic laboratories, using a number oftechnologies including chemical reduction/precipitation, ion exchange and adsorption by chitosan. Results showed that highconcentrations of 375 mg l^-1 chromium, 1,740 mg l^-1mercury and 993 mg l^-1 silver in COD wastewater can be reduced to 2.34 mg l^-1, 3.65 mg l^-1 and 1.89 mg l^-1 respectively, by the chemical reduction/precipitationprocess. Results from ion exchange at a flowrate of 20 ml min^-1 showed breakthrough effluent concentrations obtainedat 0.59 mg l^-1 chromium, 3.92 g l^-1 mercury and 0.65 mg l^-1 silver corresponding to 75.6 l at 63 hr, 40.8 l at 34 hr and 33.6 l at 28 hr respectively. Kinetic and isotherm studies revealed that chitosan can adsorb Cr⁶⁺, Hg²⁺ and Ag⁺ ions most effectively at a flowrate of 20 ml min^-1 and the optimum pH for feed solution is 4. Chitosan column experiments indicated that average effluent concentrations at breakthrough point for chromium, mercury andsilver are 0.76 mg l^-1, 6.04 mg l^-1 and 0.51 mg l^-1 respectively with throughput volumes and retention times of 120 l at 100 hr, 60 l at 50 hr and 48 l at 40 hr. Results of solidification experiments for chemical sludge and residual chitosan based on compressive strength and metal leachabilitytests showed, that the acceptable ranges of the solidificationparameters were: sludge/cement = 0.1–1.0 (weight/weight), water/cement = 0.5–0.6 (weight/weight) and sand/cement = 0.5–3.0 (weight/weight). Operating cost per litre of COD wastewater treated, based on the current prices in Thailand wasfound to be Baht 19.95 for the chemical reduction/precipitationprocess, Baht 96.35 for ion exchange treatment and Baht 18.29 forchitosan adsorption.     

Assessment of Wet Sulfate Concentration Changes at CAPMoN Sites, Canada

This paper describes a statistical analysis of wet sulfate deposition data sampled by the Canadian Air and Precipitation Monitoring Network (CAPMoN) since 1988 till 1997. The goal of the investigation is to detect presence of prevailing significant changes in the probability distribution of annual samples collected by the network at each site. The considerations are based on a first order autoregression model with second order polynomial trend and methods used for analysis of variance and multiple comparison. Unlike studies suggesting existence of long term trends in the data, methods applied here indicate absence of any systematic changes in the observed annual concentration patterns at most of the sites.     

A Statistical Assessment of Changes in Precipitation Chemistry at CAPMoN Sites, Canada

The objective of this study is to decide if chemical concentrations measured during 1988-1997in precipitation by the Canadian Air and Precipitation Monitoring Network (CAPMoN) indicate changes in the annual patterns. The inference is based on SO₄, NO₃, Cl,NH₄, Na, Ca and K concentrations monitored daily with the rain water acidity pH. By pattern is understood the probability distribution of the annual sample at a particular location. Most of the annual data can be well described by means of a linear regression model with second order polynomial trend and autocorrelated noise. Statistical analysis based on the model shows luck of systematic significant year to year increases or declines of the concentrations.     

南山雾水的采集方法及其离子浓度特征的研究

通过对2003-2005年在距新疆乌鲁木齐市58 km、海拔1 922 m的南山地区白杨沟处采集的23个雾水样品和2005年采集的7个雨水样品的分析,对静态雾水采集器的性能进行了评估.并对雾水的化学组成进行了分析讨论.     

The Influence of a Coal-Fired Power Plant in Turkey on the Chemical Composition of Rain Water in a Certain Region

In this study, the chemical composition of the rainwater in Yatağan, which is a region surrounding a coal power plant was investigated from February to April 2002. Rainwater samples were obtained from Yatağan, located northwest of Muğla City in Turkey. pH values and concentrations of major ions (Ca²⁺, Na⁺, K⁺, , , ) in the rainwater samples were analyzed. The pH varied from 5.1 to 7.9 with an average of 6.7 which was in alkaline range considering 5.6 as the neutral pH of cloud water in equilibrium with atmospheric CO₂. In the total of 30 rain events, only three events were observed with water in the acidic range (<5.6), which occurred after continuous rains. The equivalent concentration of components followed the order: Ca²⁺ > > Na⁺ > > > K⁺ > H⁺. The anion and cation concentrations in the rainwater samples showed a high sulphate concentration (131 μEq/l), as well as high sodium (40 μEq/l) and calcium (298 μEq/l) concentrations. These values indicate that one probable source of the high sodium concentration is fly ash, after the coal burning process and the power plant can be effective on level concentrations in rainwater. In addition, the dust-rich local and surrounding limestone environment might have caused the high concentration of Ca²⁺ in rainwater of the Yatağan Basin. Due to a large contribution of these cations to the sulphate neutralization action, the rainwater of this region displays only a moderate acidity, which does not cause significant environmental impact.     

离子色谱法同时测定酸雨中的钠、铵、钾、镁、钙

阐述了离子色谱法测定酸雨中的钠、铵、钾、镁、钙含量的方法和步骤。结果表明,各元素的检出限均低于0.02 mg/L,加标回收率为90%~110%,相对标准偏差均低于1%,结果令人满意。该方法可同时测定酸雨中的5种阳离子,并且操作便捷,值得推广与应用。     

2010-2015年昌吉市大气降水离子特征变化趋势研究

依据昌吉州环境监测站2010—2015年降水监测资料,分析昌吉地区降水中离子特征及变化趋势,阐明昌吉市降水污染现状及变化特征。结合昌吉市特有的气象条件、地形地貌和工业分布情况,分析污染物来源及污染变化趋势。     

Inter-Laboratory Comparison of No2 and SO2 Generated by Dynamic Dilution System Under Laboratory Conditions: A Technical Discussion

A workshop on analytical quality control (AQC) of ambient air quality measurement methods for nitrogen dioxide (NO₂) and sulphur dioxide (SO₂) was conducted by Central Pollution Control Board (CPCB) for officials involved in National Ambient Air Quality Monitoring (NAAQM) in India. Concentrations of NO₂ and SO₂ were generated by dynamic dilution system under laboratory conditions at low and high levels and measured using static dilution system and wet chemical methods laid down by CPCB under section 16(2)(h) of the air act 1981. CPCB provided the measured values as reference values for comparing the means obtained by the officials participated from thirteen organizations. A tolerance limit of ±15% of the reference values was specified to accept the results. Generated concentrations, which were unknown to the participants, were measured using gaseous sampling assembly (Envirotech APM 411, New Delhi, India), and wet chemical methods laid down by CPCB i.e. the same methodology which is used by the organizations to generate the data of NO₂ and SO₂ in ambient air. Simultaneously, concentrations were checked by CPCB using automatic analyzers as a check on reference concentration. It is observed that results of automatic analyzers for NO₂ and SO₂ were within a tolerance of ±5% with %RSD below 3. On the other hand, results of most of the participants showed variability in the measurements with %RSD ranging between ±0.8 and ±88.6 and exceedences of means from the tolerance limit with bias ranging between 1.4 and −59%. To check the cause of high variability in the measurements obtained under identical conditions, duplicate sampling was performed by one of the participants for SO₂ at low concentration level. In this study, results of wet chemical methods, automatic analyzers and results of duplicate sampling are analysed statistically to assess the cause of high variability in the measurements. Analysis of t-test and analysis of variance (ANOVA) showed highly significant results for NO₂ and SO₂ at high concentration levels (α 0.05) and for SO₂ at both the levels (α 0.01) respectively indicating some bias is existing either in the sampling or in analytical technique. Duplicate sampling performed to check precision in parallel measurements showed high %RSD indicating the presence of systematic error in sampling technique as the same calibration factor (CF) was used to measure the concentration of duplicate samples. Statistical analysis of flow rates of duplicate sampling showed that the sampling assembly could not maintain the constant flow rate within the ±10% with that measured at the start of the sampling. This resulted in high %RSD and deviation from the reference values for the results of most of the participants, even after accepting ±15% tolerance limit. There is a need to improve and evaluate this gaseous sample collection device under laboratory conditions to generate reliable database of NO₂ and SO₂ in ambient air.     

Statistical Analysis of Spatial Pattern: A Comparison of Grid and Hierarchical Sampling Approaches

Previous studies have combined random-site hierarchical sampling designs with analysis of variance techniques, and grid sampling with spatial autocorrelation analysis. We illustrate that analysis techniques and sampling designs are interchangeable using densities of an infaunal bivalve from a study in Poverty Bay, New Zealand. Hierarchical designs allow the estimation of variances associated with each level, but high-level factors are imprecisely estimated, and they are inefficient for describing spatial pattern. Grid designs are efficient for describing spatial pattern, and are amenable to conventional analysis. Our example deals with a continuous spatial habitat, but our conclusions also apply in disjunct or patchy habitats. The influence of errors in positioning is also assessed. The advantages of systematic sampling are reviewed, and more efficient hierarchical approaches are identified. The distinction between biological and statisticalsignificance in all analyses is emphasised.     

Testing the validity of a critical sulfur and nitrogen load model in southern Ontario, Canada, using soil chemistry data from MARYP

The validity of a steady-state massbalance model (Arp et al., 1996; referred to asARP) was tested using physicochemical soil data fromthe Monitoring Acid Rain Youth Program (MARYP). FourARP sites were matched with ten MARYP sites accordingto proximity, bedrock type and subsoil pH to test thevalidity of the ARP model for critical loadexceedances. Soil solution pH, base concentration andAl concentration from MARYP sites, which were wellmatched to ARP sites, validated the modelled criticalload exceedances. Higher exceedance areas wereassociated with more acidic pH and lower base andhigher Al concentrations from matched MARYP sites andvice versa. One ARP site was inappropriately matchedwith MARYP sites and could not be validated using baseand Al concentrations. This study also confirmed thesouthern limit of the zero critical load exceedanceisopleth from the model. However, variability of theother exceedance isopleths was noted due to thelimited number of sites used in the model. Thevalidation of these sites in the ARP model and thezero critical load exceedance isopleth nonethelessallows greater confidence in using this model as amanagement tool for acidic deposition.