Heavy metal contamination in surface sediments of Yangtze River intertidal zone: An assessment from different indexes

Surface sediments (0-5 cm) from 59 stations within the Yangtze River intertidal zone (YRIZ) were sampled for metal contamination analysis in April and August 2005. The concentrations ranged (in mg kg⁻¹ dry weight): Al, 40,803-97,213; Fe, 20,538-49,627; Cd, 0.12-0.75; Cr, 36.9-173; Cu, 6.87-49.7; Mn, 413-1,112; Ni, 17.6-48.0; Pb, 18.3-44.1; and Zn, 47.6-154; respectively. Among the 59 sampling stations, enrichment factors (EF) indicate enrichment of Cd (52 stations), Cr (54 stations), Cu (5 stations), Ni (26 stations), Pb (5 stations) and Zn (5 stations). Geoaccumulation indexes (I_geo) also suggest individual metal contamination in localized areas. This study indicates that Cd, Cr and Ni enrichment in the YRIZ sediment is widespread whereas Cu, Mn, Pb and Zn enrichment is localized or nonexistent. Factor and cluster analyses indicate that Cd is associated with total organic carbon whereas Cu, Cr, Ni, Pb and Zn have a close association with Mn.     

Status of metal levels and their potential sources of contamination in Southeast Asian rivers

To assess the concentration and status of metal contaminants in four major Southeast Asian river systems, water were collected from the Tonle Sap–Bassac Rivers (Cambodia), Citarum River (Indonesia), lower Chao Phraya River (Thailand), and Saigon River (Vietnam) in both dry and wet seasons. The target elements were Be, Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Ba, Tl, and Pb and the concentrations exceeded the background metal concentrations by 1- to 88-fold. This distinctly indicates enrichment by human urban area activities. The results of a normalization technique used to distinguish natural from enriched metal concentrations confirmed contamination by Al, Cd, Co, Mn, Ni, Pb, and Zn. Cluster analysis revealed the probable source of metals contamination in most sampling sites on all rivers studied to be anthropogenic, including industrial, commercial, and residential activities. Stable lead isotopes analyses applied to track the sources and pathways of anthropogenic lead furthermore confirmed that anthropogenic sources of metal contaminated these rivers. Discharges of wastewater from both industrial and household activities were major contributors of Pb into the rivers. Non-point sources, especially road runoff and street dust, also contributed contamination from Pb and other metals.     

Heavy metals in sediments,soils, and aquatic plants from a secondary anabranch of the three gorges reservoir region,China

We investigated the occurrence of cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), Znic (Zn), iron (Fe), manganese (Mn), and magnesium (Mg) in sediments, as well as in related soils and aquatic plants in the Liangtan River, a typical secondary anabranch of the Yangtze River in the Three Gorges Reservoir Region (TGRR) of China. We found that sediments accumulated more metals than soils and aquatic plants. Concentrations of the nine metals in sediments and soils followed the same sequence, while their concentrations in aquatic plants followed a different sequence. Potential adverse effects of contaminated sediments on benthic fauna were evaluated, and the results showed that the toxic effect on benthic organisms followed the sequence Zn?>?Ni?>?Cr?>?Cu?>?Cd?>?Pb. The potential ecological risk index analysis indicated that Cd in sediments had considerable ecological risk, whereas Cr, Cu, Zn, Ni, and Pb had low ecological risk. The potential ecological risk index (RI) of the heavy metals in sediments of the Liangtan River was 174.9, indicating moderate ecological risk. The transfer factor trend of metals for aquatic plants showed that Cd and Ni had the most and least accumulation, respectively. For Cu, Cd, Mg, Pb, and Cr, a significant positive correlation of the metal concentrations was observed between sediments and soils, but no correlations (excluding Cr) were detected between sediments and aquatic plants. Our study indicated that anthropogenic input may be the primary source of metal contamination in the Liangtan River, and that Zn and Cd pollution in the Liangtan River should be further explored.     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

Multivariate analysis of mineral constituents of edible Parasol Mushroom (Macrolepiota procera) and soils beneath fruiting bodies collected from Northern Poland

Caps and stipes of 141 fruiting bodies of Parasol Mushroom (Macrolepiota procera) and surface layer of soils collected from 11 spatially distant and background (pristine) areas in Northern Poland were analyzed for Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr, and Zn by inductively coupled plasma optical emission spectroscopy and cold vapor atomic absorption spectroscopy. In terms of bioconcentration and bioexclusion concept, K, Ag, Cu, Rb, and P were highly bioconcentrated in caps, and their bioconcentration factor values varied for the 11 sites between 120 and 500—67–420, 70–220, 10–170, and 45–100, respectively. Cd, Zn, Mg, and Na showed bioconcentration factors (BCFs) between 3.3 and 36, 3.7–15, 0.92–6.3, and 1.4–44 while Al, Ba, Ca, Co, Cr, Mn, Ni, Pb, and Sr were excluded (BCF < 1). The Parasol Mushroom is a species harvested in the wild, and its caps are of unique taste and can contain a spectrum of essential and hazardous mineral compounds accumulated at elevated concentrations, even if collected at the background (pristine) areas. These elevated mineral concentrations of the caps are due to the efficient bioconcentration potential of the species (K, Ag, Cu, Rb, P, Cd, Zn, Mg, and Na) and abundance in the soil substrates (Al, Ca, Fe, Mn). The estimated intake rates of Cd, Hg, and Pb contained in Parasol Mushroom’s caps show a cause for concern associated with these metals resulting from the consumption of between 300- and 500-g caps daily, on a frequent basis in the mushrooming season.     

Temporal variability in 20 chemical elements content of Parasol Mushroom (Macrolepiota procera) collected from two sites over a few years

Mature specimens of Parasol Mushroom were collected annually in the outskirts of the Siemiany (2000-2003) and Rafa (2001-2003) sites in the northern part of Poland to examine temporal variations and similarities in the composition of 20 chemical elements. Analysis was done under the same condition and using well-validated analytical methods. Elements were determined by inductively coupled plasma-atomic emission spectroscopy and cold vapour-atomic absorption spectroscopy (Hg). The ranges of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn concentrations in the caps of fruiting bodies were similar (p > 0.05; Mann-Whitney U test) for both geographically distant sites, and these specimens from Rafa were more contaminated with Pb (p < 0.05; Mann-Whitney U test). The annual collections of caps in the Siemiany site varied in Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, Na, Rb and Sr and contents (0.05 < p < 0.001), while they were similar in Cr, K, Mg, Mn, Ni, P, Pb and Zn (p > 0.05; Mann-Whitney U test). The annual collections of specimens from the Rafa site varied in contents of Ag, Al, Ba, Ca, Fe, Hg, K, Mg, Mn, P, Rb and Zn (p > 0.05), while they were similar in Cd, Co, Cr, Cu, Na, Ni, Pb and Sr (p < 0.05). The results of this study imply that metallic elements content of Parasol Mushroom collected at the same undisrupted sites, and hence keeping the same geochemical condition for mushroom development and fructification (the same stands and probably the same mycelia), can fluctuate over the years or the life-span of mycelium. Hence, when assessing the nutritional value of essential metallic elements and status of non-essential or toxic metallic elements in Parasol's Mushroom caps (and probably also of other mushrooms species) to man, the possible fluctuation in contents over time have to be taken into account.     

应用地质累积指数评价抚顺市PM10中元素的污染

2006-2007年采暖季、风沙季和非采暖季分别在抚顺市的6个采样点采集PM10样品,用等离子体原子发射光谱(ICP-AES)法测定样品中Ti、Al、Mn、Mg、Ca、Na、K、Cu、Zn、As、Pb、Cr、Ni、Co、Cd、Fe、V等17种元素的含量,并用地质累积指数对其污染状况进行初步评价。结果表明:(1)从PM10中元素在不同采样点的含量看,抚顺市PM10中Ti、Mn、Mg、Cu、Zn、Pb、Cr、Ni、Co这9种元素在各采样点间的差别较大;Al、Ca、Na、K、As、Cd、Fe、V这8种元素差别较小。(2)从PM10中元素在不同采样季的含量看,抚顺市PM10中Mn、Mg含量的季间差别较大,其余15种元素季间差别较小。(3)Zn、Cd污染较重;Ti、Al、Mg、Ca、Na、K、As、Fe和V污染较轻;其他6种元素在6个采样点和3个采样季污染程度差别较大。(4)水库采样点各元素污染级别均不是最高;新华采样点PM10中Cu、Zn、Pb、Cr、Ni、Co、Cd污染级别均较高。(5)3个采样季PM10中Cd、Zn污染均较重,属于重度或严重污染;在采暖季PM10中Cu、Pb、Cr的地质累积指数较风沙季、非采暖季大;在非采暖季PM10中Mn、Co受到的污染比采暖季和风沙季稍严重。     

Influence of solution acidity and CaCl2 concentration on the removal of heavy metals from metal-contaminated rice soils

Soil washing is considered a useful technique for remediating metal-contaminated soils. This study examined the release edges of Cd, Zn, Ni, Cr, Cu or Pb in two contaminated rice soils from central Taiwan. The concentrations exceeding the trigger levels established by the regulatory agency of Taiwan were Cu, Zn, Ni and Cr for the Ho-Mei soil and Pb for the Nan-Tou soil. Successive extractions with HCl ranging from 0 to 0.2 M showed increased release of the heavy metals with declining pH, and the threshold pH value below which a sharp increase in the releases of the heavy metals was highest for Cd, Zn, and Ni (pH 4.6 to 4.9), intermediate for Pb and Cu (3.1 to 3.8) and lowest for Fe (2.1), Al (2.2) and Cr (1.7) for the soils. The low response slope of Ni and Cr particularly for the rice soils make soil washing with the acid up to the highest concentration used ineffective to reduce their concentrations to below trigger levels. Although soil washing with 0.1 M HCl was moderately effective in reducing Cu, Pb, Zn and Cd, which brought pH of the soils to 1.1+/-0.1 (S.D.), the concurrent release of large quantities of Fe and Al make this remediation technique undesirable for the rice soils containing high clay. Successive washings with 0.01 M HCl could be considered an alternative as the dissolution of Fe and Al was minimal, and between 46 to 64% of Cd, Zn, and Cu for the Ho-Mei soil and 45% of Pb in the Na-Tou soil were extracted after four successive extractions with this dilute acid solution. The efficacy of Cd extraction improved if CaCl2 was added to the acid solution. The correlation analysis revealed that Cr extracted was highly correlated (P < 0.001) with Fe extracted, whereas the Cu, Ni, Zn, Cd or Pb extracted was better correlated (P < 0.001) with Al than with Fe extracted. It is possible that the past seasonal soil flooding and drainage in the soils for rice production was conducive to incorporating Cr within the structure of Fe oxide, thereby making them extremely insoluble even in 0.2 M HCl solution. The formation of solid solution of Ni with Al oxide was also possible, making it far less extractable than Cd, Zn, Cu, or Pb with the acid concentrations used.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Accumulation of selected metals and concentration of macroelements in liver and kidney tissues of sympatric golden jackal (Canis aureus) and red fox (Vulpes vulpes) in Somogy County,Hungary

Environmental Science and Pollution Research - This study examined the concentrations of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and Zn in the liver and kidney samples of golden jackals (n =...     

Analysis of essential and non-essential trace elements in the organs of a mother–fetus pair of spotted seals (Phoca largha) from the Sea of Japan

Environmental Science and Pollution Research - Concentrations of 22 essential and non-essential trace elements (Be, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sb, Ba, Tl, Pb, Th, U, and...     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd) and Al concentrations as well as values of Ca/Al in the tip, middle, base sections and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Distribution of elements in needles of Pinus massoniana (Lamb.) was uneven and affected by needle age

Macronutrients (P, S, K, Na, Mg, Ca), heavy metals (Fe, Zn, Mn, Cu, Pb, Cr, Ni, Cd,) and Al concentrations as well as values of Ca/Al in the tip, middle and base sections, and sheaths of current year and previous year needles of Pinus massoniana from Xiqiao Mountain were analyzed and the distribution patterns of those elements were compared. The results indicated that many elements were unevenly distributed among the different components of needles. Possible deficiency of P, K, Ca, Mn and Al toxicity occurred in needles under air pollution. Heavy metals may threaten the health of Masson pine. Needle sheaths were good places to look for particulate pollutants, in this case including Fe, Cu, Zn, Pb, Cr, Cd and Al.     

Metals in edible fish from Vistula River and Dead Vistula River channel, Baltic Sea

Metals including Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Na, Ni, Pb, Sr and Zn were determined in muscle tissue of 12 fish species by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) and cold vapour-atomic absorption spectroscopy (CV-AAS). Fish were collected from Vistula River at lower course and Dead Vistula River channel in south of Baltic Sea in Poland. The fish species examined include Round Goby (Neogobius melanostomus), Crucian Carp (Carassius carassius), Bull-rout (Myoxocephalus scorpius), Tench (Tinca tinca), Bream (Abramis brama), Burbot (Lota lot), Perch (Perca perca), Roach (Rutilus rutilus), Silver Carp (Hypophthalmichthys molitrix), Pikeperch (Stizostediun lucioperca), Brown salmon (Salmo trutta m. Trutta) and Eel (Anguilla anguilla). The median values of metal concentrations in fresh muscle tissue of 11 fish species varied as follows: Al < 0.5-60; Ba < 0.05-0.31; Ca 120-1800; Cd < 0.05-0.096; Co < 0.10; Cr < 0.10-0.50; Cu < 0.15-0.77; Fe 1.5-21; Hg 0.0058-0.65; K 1800-4200; Mg 130-560; Mn 0.12-0.59; Na 350-840; Ni < 0.2-0.31; Pb < 0.75; Sr 0.079-2.9; Zn 3.3-23 μg/g fresh weight. The Target Hazard Quotient (THQ) values calculated in this study for Cd and Hg from muscles of fish species collected from Vistula River were low in the range of 0.4 for Hg and 0.8 for Cd.     

Non-destructive pollution exposure assessment in the European hedgehog (Erinaceus europaeus): II. Hair and spines as indicators of endogenous metal and As concentrations

The role of hair and spines of the European hedgehog as non-destructive monitoring tools of metal (Ag, Al, Cd, Co, Cr, Cu, Fe, Ni, Pb, Zn) and As pollution in terrestrial ecosystems was investigated. Our results showed that mean pollution levels of a random sample of hedgehogs in Flanders are low to moderate. Yet, individual hedgehogs may be at risk for metal toxicity. Tissue distribution analyses (hair, spines, liver, kidney, muscle and fat tissue) indicated that metals and As may reach considerable concentrations in external tissues, such as hair and spines. Positive relationships were observed between concentrations in hair and those in liver, kidney and muscle for Al, Co, Cr, Cu, and Pb (0.43 < r < 0.85). Spine concentrations were positively related to liver, kidney and muscle concentrations for Cd, Co, Cr, Cu and Pb (0.37 < r < 0.62). Hair Ag, As, Fe and Zn and spine Ag, Al, As and Fe were related to metal concentrations in one or two of the investigated internal tissues (0.31 < r < 0.45). The regression models presented here may be used to predict metal and As concentrations in internal tissues of hedgehogs when concentrations in hair or spines are available. The present study demonstrated the possibility of using hair and spines for non-destructive monitoring of metal and As pollution in hedgehogs.     

Temporal variability in 20 chemical elements content of Parasol Mushroom (Macrolepiota procera) collected from two sites over a few years

Mature specimens of Parasol Mushroom were collected annually in the outskirts of the Siemiany (2000–2003) and Rafa (2001–2003) sites in the northern part of Poland to examine temporal variations and similarities in the composition of 20 chemical elements. Analysis was done under the same condition and using well-validated analytical methods. Elements were determined by inductively coupled plasma–atomic emission spectroscopy and cold vapour–atomic absorption spectroscopy (Hg). The ranges of Ag, Al, Ba, Ca, Cd, Co, Cu, Cr, Fe, Hg, K, Mg, Mn, Na, Ni, P, Pb, Rb, Sr and Zn concentrations in the caps of fruiting bodies were similar (p > 0.05; Mann-Whitney U test) for both geographically distant sites, and these specimens from Rafa were more contaminated with Pb (p < 0.05; Mann-Whitney U test). The annual collections of caps in the Siemiany site varied in Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, Hg, Na, Rb and Sr and contents (0.05 < p < 0.001), while they were similar in Cr, K, Mg, Mn, Ni, P, Pb and Zn (p > 0.05; Mann-Whitney U test). The annual collections of specimens from the Rafa site varied in contents of Ag, Al, Ba, Ca, Fe, Hg, K, Mg, Mn, P, Rb and Zn (p > 0.05), while they were similar in Cd, Co, Cr, Cu, Na, Ni, Pb and Sr (p < 0.05). The results of this study imply that metallic elements content of Parasol Mushroom collected at the same undisrupted sites, and hence keeping the same geochemical condition for mushroom development and fructification (the same stands and probably the same mycelia), can fluctuate over the years or the life-span of mycelium. Hence, when assessing the nutritional value of essential metallic elements and status of non-essential or toxic metallic elements in Parasol's Mushroom caps (and probably also of other mushrooms species) to man, the possible fluctuation in contents over time have to be taken into account.     

An ozone flux-response relationship for wheat

The concentrations of heavy metals in the fine fraction (<63 microm) of 19 surficial sediment samples from the border region of Baja California (Mexico) and California (USA) were determined. The concentration ranges (in microg g(-1)) of the metals were: Cu, 4.9-23; Zn, 39-188; Ni, 16-44; Cr, 56-802; Pb, 6-21; Cd, 0.08-0.64; Ag, 0.01-0.28; and Mn, 392-1506; the intervals (percentage) for Fe and Al were 1.36-4.6 and 3.61-8.55, respectively. The heavy metals in these sediments indicate a relative enrichment of Cr (>3000%), Zn (>350%), Ni (>300%) and Cu (>150%) off the wastewater outfall at Punta Bandera in Tijuana, Baja California, with respect to non-polluted sediments of the region. Pb, Cd and Ag have low concentrations off the same outfall and enrichment factors are generally lower than 300% (Pb) and lower than 150% (Cd and Ag). This suggests that these metals have a different origin, or that they are controlled by a different geochemical mechanism than the former. The concentrations of Mn, Fe and Al occurred within ranges typical for coastal areas and probably reflect the mineralogical composition of the sediments of the region.     

Concentrations,spatial distribution,and pollution assessment of heavy metals in surficial sediments from upstream of Yellow River,China

Surface sediments were collected from 122 sites in the upstream of the Yellow River, China. The concentration of Fe, Mn, Cu, Ni, Zn, Cr, Pb, and Cd in sediments was investigated to explore the spatial distribution based on statistics and interpolation method. The results suggested that the concentrations of heavy metals were lower than potential effect levels (PEL). The samples above threshold effect level (TEL) for Pb and Zn were less than 10%, while almost 50% of samples for Ni exceeded PEL. Pb and Zn in sediments performed little or no adverse effects on the aquatic ecosystems. Higher concentrations of all heavy metals occurred in Qinghai and Gansu sections; the concentrations of Cu, Ni, and Zn were significantly higher than the Inner Mongolia section. Lower concentration of Fe, Mn, Cu, Ni, and Zn appeared in Qinghai section; the concentrations of Fe, Mn, Cr, and Pb manifested relatively steady and similar distributions and approximately decreasing tendency along the upstream of Yellow River.

     

Anthropogenic metal enrichment of snow and soil in north-eastern European Russia

Trace metal composition of winter snowpack, snow-melt filter residues and top-soil samples were determined along three transects through industrial towns in the Usa basin, North-East Russia: Inta, Usinsk and Vorkuta. Snow was analysed for Ag, Al, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Sr and Zn using ICP-MS (Ca and K by F-AAS for Vorkuta only), pH and acidity/alkalinity. Filter residues were analysed for: Al, Ba, Ca, Cd, Cu, K, Mg, Mn, Ni, Pb, Sr and Zn using F-AAS and GF-AAS; top-soil samples were analysed for Ba, Cu, Mg, Mn, Na, Ni, Pb, Sr, Zn using F-AAS. Results indicate elevated concentrations of elements associated with alkaline combustion ash around the coal mining towns of Vorkuta and Inta. There is little evidence of deposition around the gas and oil town of Usinsk. Atmospheric deposition in the vicinity of Vorkuta, and to a lesser extent Inta, added significantly to the soil contaminant loading as a result of ash fallout. Acid deposition was associated with pristine areas whereas alkaline combustion ash near to emission sources more than compensated for the acidity caused by SO2.